Phase change inks containing compounds derived from isocyanate, unsaturated alcohol, and polyol

ABSTRACT

Disclosed is a phase change ink comprising a colorant, an initiator, and a phase change ink carrier, said carrier comprising (A) a first isocyanate-derived compound which is the reaction product of a mixture comprising (1) an isocyanate; and (2) a component comprising (a) an alcohol having at least one ethylenic unsaturation; (b) an amine having at least one ethylenic unsaturation; (c) an acid having at least one ethylenic unsaturation; or (d) mixtures thereof, (B) a second isocyanate-derived compound which is the reaction product of (1) a diisocyanate; (2) a monoalcohol having exactly one hydroxyl group and having at least one ethylenic unsaturation; and (3) a polyol having two or more hydroxyl groups, (C) an optional phase change inducing component, said phase change inducing component containing at least one hydroxyl group, said phase change inducing component having a melting point of about 40° C. or higher, and (D) an optional curable viscosity modifying ester, said ink being curable upon exposure to ultraviolet radiation.

CROSS-REFERENCE TO RELATED APPLICATIONS

Copending application U.S. Ser. No. 11/018,378, filed Dec. 22, 2004,entitled “Curable Phase Change Ink Composition,” with the namedinventors Peter G. Odell, Marcel P. Breton, Christine E. Bedford, andChris A. Wagner, the disclosure of which is totally incorporated hereinby reference, discloses ink compositions that comprise one or moreradiation curable oil soluble components and one or more thermalsolvents, as well as methods of preparing such ink compositions andmethods of using such ink compositions.

Copending application U.S. Ser. No. 11/034,714, filed Jan. 14, 2005,entitled “Ink Jet Ink of Functionalized Waxes,” with the named inventorsJennifer L. Belelie, Peter G. Odell, Eniko Toma, Paul F. Smith, and RinaCarlini, the disclosure of which is totally incorporated herein byreference, discloses an ink jet ink including an ink vehicle wherein theink vehicle includes at least one wax monomer functionalized to includein the chain at least one reactive group curable upon exposure toradiation. The reactive group is preferably curable via cationic or freeradical polymerization. In a preferred embodiment, the ink vehicleincludes a wax monomer having a structure:

wherein C represents a cationically curable group and R represents aradically curable group. The inks may be used to form an image byjetting the ink onto a transfuse member surface, increasing theviscosity of the ink upon the transfuse member surface, subsequentlytransferring the ink from the transfuse member surface to an imagereceiving substrate, and exposing the ink to radiation following thetransfer to the image receiving substrate to effect reaction of the atleast one reactive group.

Copending application U.S. Ser. No. (not yet assigned; Attorney DocketNumber 20030890-US-NP), filed concurrently herewith, entitled “PhaseChange Inks Containing Curable Isocyanate-Derived Compounds,” with thenamed inventors Jeffery H. Banning, Jennifer L. Belelie, Peter G. Odell,Rina Carlini, Jule W. Thomas, Donald R. Titterington, Paul F. Smith,Stephan V. Drappel, and Chris Wagner, the disclosure of which is totallyincorporated herein by reference, discloses a phase change inkcomprising a colorant, an initiator, and a phase change ink carrier,said carrier comprising (A) a urethane which is the reaction product ofa mixture comprising (1) an isocyanate; and (2) an alcohol selected fromthe group consisting of 1,4 butanediol vinyl ether, 2-allyloxy ethanol,1,4-cyclohexanedimethanol vinyl ether, ethylene glycol vinyl ether,di(ethylene glycol) vinyl ether, and mixtures thereof; (B) a compoundwhich is the reaction product of a mixture comprising (1) an isocyanate;and (2) a component comprising (a) an amine having at least oneethylenic unsaturation; (b) an acid having at least one ethylenicunsaturation; (c) a mixture of an amine having at least one ethylenicunsaturation and an alcohol having at least one ethylenic unsaturation;(d) a mixture of an acid having at least one ethylenic unsaturation andan alcohol having at least one ethylenic unsaturation; or (e) mixturesthereof; or (C) a mixture of (A) and (B); said ink being curable uponexposure to ultraviolet radiation.

Copending application U.S. Ser. No. (not yet assigned; Attorney DocketNumber 20031170-US-NP), filed concurrently herewith, entitled “PhaseChange Inks Containing Curable Isocyanate-Derived Compounds and PhaseChange Inducing Components,” with the named inventors Jennifer L.Belelie, Peter G. Odell, Marcel P. Breton, Jeffery H. Banning, StephanV. Drappel, and Chris Wagner, the disclosure of which is totallyincorporated herein by reference, discloses a phase change inkcomprising a colorant, an initiator, and a phase change ink carrier,said carrier comprising (A) a compound which is the reaction product ofa mixture comprising (1) an isocyanate; and (2) a component comprising(a) an alcohol having at least one ethylenic unsaturation; (b) an aminehaving at least one ethylenic unsaturation; (c) an acid having at leastone ethylenic unsaturation; or (d) mixtures thereof, (B) a phase changeinducing component, said phase change inducing component containing atleast one hydroxyl group, said phase change inducing component having amelting point of about 40° C. or higher, and (C) an optional curableviscosity modifying ester, said ink being curable upon exposure toultraviolet radiation.

Copending application U.S. Ser. No. (not yet assigned; Attorney DocketNumber 20041459-US-NP), filed concurrently herewith, entitled “CurableOvercoat for Wax-Based Inks,” the disclosure of which is totallyincorporated herein by reference, discloses an ink jettable overprintcomposition including at least one of a polymerizable monomer and/or apolymerizable oligomer, at least one photoinitiator, and at least onewax.

Copending application U.S. Ser. No. (not yet assigned; Attorney DocketNumber 20040221-US-NP), filed concurrently herewith, entitled “CurablePhase Change Compositions and Methods for Using Such Compositions,” thedisclosure of which is totally incorporated herein by reference,discloses a phase change curable composition comprising curable monomer,photoinitiator that initiates polymerization of the curable monomer, andphase change agent that provides the composition with an increase inviscosity of at least four orders of magnitude, from a firsttemperature, the first temperature being from 50° C. to 130° C., to asecond temperature, the second temperature being from 0° C. to 70° C.,wherein the second temperature is at least 10° C. below the firsttemperature. A coating over an image may be applied by providing acomposition comprising curable monomer at a first temperature; applyingthe composition over the image, the image being at a second temperature;and exposing the composition to radiation to initiate polymerization ofthe curable monomer. In this process, the composition has a viscosity atthe second temperature that is at least four orders of magnitude greaterthan its viscosity at the first temperature.

BACKGROUND

Disclosed herein are phase change inks containing isocyanate-basedcurable compounds. More specifically, disclosed herein are phase changeinks containing isocyanate-based curable amides, ureas, urethanes,urea/urethanes, amide/urethanes, and the like. One embodiment isdirected to a phase change ink comprising a colorant, an initiator, anda phase change ink carrier, said carrier comprising (A) a firstisocyanate-derived compound which is the reaction product of a mixturecomprising (1) an isocyanate; and (2) a component comprising (a) analcohol having at least one ethylenic unsaturation; (b) an amine havingat least one ethylenic unsaturation; (c) an acid having at least oneethylenic unsaturation; or (d) mixtures thereof, (B) a secondisocyanate-derived compound which is the reaction product of (1) adiisocyanate; (2) a monoalcohol having exactly one hydroxyl group andhaving at least one ethylenic unsaturation; and (3) a polyol having twoor more hydroxyl groups, (C) an optional phase change inducingcomponent, said phase change inducing component containing at least onehydroxyl group, said phase change inducing component having a meltingpoint of about 40° C. or higher, and (D) an optional curable viscositymodifying ester, said ink being curable upon exposure to ultravioletradiation.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 6,048,925 (Titterington et al.), the disclosure of whichis totally incorporated herein by reference, discloses urethane resinsmade by reacting selected nucleophiles, including alcohols, with anisocyanate. The order of addition of the isocyanate and the differentnucleophiles can tailor the distribution of mixed urethane molecules inthe final resin product. The final resin product can be colored oruncolored and include a toughening agent. The isocyanate-derived resinmaterials are useful as ingredients as phase change ink carriercompositions used to make phase change ink jet inks.

U.S. Pat. No. 5,919,839 (Titterington et al.), the disclosure of whichis totally incorporated herein by reference, discloses colored waxesmade by reacting selected nucleophiles, including alcohol containingcolorants with an isocyanate. A phase change ink is made by blending thecolored wax with a clear ink carrier composition. The clear ink carriercomposition can be a fatty amide-based material and/or a combination ofisocyanate-derived resins in which the order of addition of theisocyanate and the different nucleophiles can tailor the distribution ofdi-urethane, mixed urethane/urea, and/or di-urea molecules in the finalresin product. The colored wax materials are useful as ingredients withphase change ink carrier compositions to make phase change ink jet inks.

U.S. Pat. No. 5,830,942 (King et al.), the disclosure of which istotally incorporated herein by reference, discloses resins and waxesmade by reacting selected nucleophiles, including alcohols and/oramines, with an isocyanate. The order of addition of the isocyanate, andthe different nucleophiles can tailor the distribution of diurethane,mixed urethane/urea, and/or di-urea molecules in the final resinproduct. The isocyanate-derived resin and wax materials are useful asingredients as phase change ink carrier compositions used to make phasechange ink jet inks.

U.S. Pat. No. 5,827,918 (Titterington et al.), the disclosure of whichis totally incorporated herein by reference, discloses resins and waxesmade by reacting selected nucleophiles, including alcohols and/oramines, with an isocyanate. The order of addition of the isocyanate andthe different nucleophiles can tailor the distribution of diurethane,mixed urethane/urea, and/or di-urea molecules in the final resinproduct. The isocyanate-derived resin and wax materials are useful asingredients as phase change ink carrier compositions used to make phasechange ink jet inks.

U.S. Pat. No. 5,783,658 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses resins and waxesmade by reacting selected nucleophiles, including alcohols and/oramines, with an isocyanate. The order of addition of the isocyanate andthe different nucleophiles can tailor the distribution of di-urethane,mixed urethane/urea, and/or di-urea molecules in the final resinproduct. The isocyanate-derived resin and wax materials are useful asingredients as phase change ink carrier compositions used to make phasechange ink jet inks.

U.S. Pat. No. 5,782,966 (Bui et al.), the disclosure of which is totallyincorporated herein by reference, discloses resins and waxes made byreacting selected nucleophiles, including alcohols and/or amines, withan isocyanate. The order of addition of the isocyanate and the differentnucleophiles can tailor the distribution of di-urethane, mixedurethane/urea, and/or di-urea molecules in the final resin product. Theisocyanate-derived resin and wax materials are useful as ingredients asphase change ink carrier compositions used to make phase change ink jetinks.

U.S. Pat. No. 5,780,528 (Titterington et al.), the disclosure of whichis totally incorporated herein by reference, disclosesisocyanate-derived colored resins made by reacting an alcohol and/oramine, an isocyanate and a nucleophilic molecule containing a chromogen.The isocyanate-derived colored resins are useful as colorant materialsin phase change ink compositions.

U.S. Pat. No. 5,750,604 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses resins and waxesmade by reacting selected nucleophiles, including alcohols and/oramines, with an isocyanate. The order of addition of the isocyanate andthe different nucleophiles can tailor the distribution of di-urethane,mixed urethane/urea, and/or di-urea molecules in the final resinproduct. The isocyanate-derived resin and wax materials are useful asingredients as phase change ink carrier compositions used to make phasechange ink jet inks.

PCT Patent Publication WO 94/14902 (Griffiths et al.), the disclosure ofwhich is totally incorporated herein by reference, discloses a materialsuitable for use in a hot melt ink, having a melting point of at least65° C. and obtainable by reacting an aliphatic or aromatic diisocyanatewith an at least stoichiometric amount of: (i) a monohydric alcoholcomponent; or (ii) a monohydric alcohol component followed by anotherdifferent monohydric alcohol component; or (iii) a monohydric alcoholcomponent, followed by a dihydric alcohol component followed by amonohydric alcohol component; the monohydric alcohol component(s)comprising a monohydric aliphatic alcohol or an etherified or esterifieddihydric aliphatic alcohol or dihydric polyalkylene glycol; as thedihydric alcohol component comprising a dihydric aliphatic alcohol or adihydric polyalkylene glycol and being used in an amount of not morethan 50 percent of the stoichiometric amount of hydroxyl groups requiredto react with the isocyanate groups on the diisocyanate.

U.S. Pat. No. 6,534,128 (Carlson et al.), the disclosure of which istotally incorporated herein by reference, discloses low viscosity,radiation curable urethane oligomers, preferably a radiation curablepolyester urethane oligomer, that can be incorporated into radiationcurable ink compositions. Preferred embodiments are suitable for inkjetting applications. The ink jettable embodiments are particularlywell-suited for use in piezo ink jet printers. The viscositycharacteristics of the compositions are such that conventional solventis not required in order to satisfy the requisite low ink jet viscosityspecifications. The oligomer generally is a reaction product ofingredients comprising an aliphatic polyisocyanate; and a radiationcurable, polyester alcohol comprising one or more radiation curablemoieties, one or more hydroxyl moieties, and one or more ester moieties.

U.S. Pat. No. 6,586,492 and PCT Patent Publication WO 99/54416 (Caigeret al.), the disclosures of each of which are totally incorporatedherein by reference, disclose an ink-jet ink including an ink jetvehicle and a colorant. The vehicle includes at least 35 percent byweight radiation curable material, based on the total vehicle weight.The vehicle may but does not necessarily include a thickener. Thevehicle is a paste or a solid at 20° C. and has a viscosity of less than25 centipoise between 40° C. and 130° C.

U.S. Pat. No. 6,410,611 and European Patent Publication EP 0 878 482(Sakurai et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose an active energy ray curablecomposition which can be cured in the absence of a photoinitiator andwhich can also be cured at practical light intensities and irradiatingenergy, and a method for curing the curable composition, in which thecomposition comprises a maleimide derivative represented by the formula

wherein m and n each represent an integer of 1 to 5, and the total of mand n is 6 or smaller, R₁₁ and R₁₂ each represent a linking groupselected from the group consisting of (1) an alkylene group, (2) analicyclic group, (3) an arylalkylene group, and (4) a cycloalkylalkyenegroup, G₁ and G₂ each represent an ester linkage selected from the groupconsisting of —COO— and —OCO—, R₂ represents a linking chain having anaverage molecular weight of 100 to 100,000 selected from the groupconsisting of (A) a (poly)ether linking chain and (B) a (poly)esterlinking chain, in which at least one organic group selected from thegroup consisting of (1) a straight chain alkylene group, (2) a branchedalkylene group, (3) an alkylene group having a hydroxyl group, (4) analicyclic group, (5) an aryl group, and (6) an arylalkylene group isconnected via at least one linkage selected from the group consisting of(a) an ether linkage and (b) an ester linkage.

Japanese Patent Publication JP 6200204, the disclosure of which istotally incorporated herein by reference, discloses a normally solid jetrecording ink which can melt at a relatively low temperature and cancure immediately when irradiated with ultraviolet rays. The inkcomprises a wax having a melting point of 40 to 70° C., a resin having amelting point of 40 to 70° C., a prepolymer, a monomer, aphotopolymerization initiator, a dye, and a pigment. This ink isnormally solid because it contains the above-specified wax. When theultraviolet curable resin is irradiated with ultraviolet rays from anultraviolet lamp, the ink can fix immediately and satisfactorily onplain paper or printing paper.

U.S. Patent Publication 2003/0232926 and European Patent Publication EP1 362 901 (Nikolic et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose a film adhesive prepared froman adhesive composition comprising a polymer system, a film formingrubber compound, and curing agents for the polymeric system. The polymersystem comprises a base polymer and electron donor and electron acceptorfunctionality.

U.S. Pat. No. 5,693,128 (Sacripante et al.), the disclosure of which istotally incorporated herein by reference, discloses an ink compositioncomprising a colorant and a reversible crosslinked component vehicleobtained from the reaction product of an anhydride and an organoamine,which ink possesses a viscosity of from about 1 centipoise to about 25centipoise at a temperature of from about 125° C. to about 185° C.

While known compositions and processes are suitable for their intendedpurposes, a need remains for improved phase change ink compositions. Inaddition, a need remains for phase change inks that produce images withimproved scratch resistance. Further, a need remains for phase changeinks that produce images with improved adhesion to substrates such aspaper. Additionally, a need remains for ultraviolet curable compoundsthat are soluble in phase change ink carriers. There is also a need forultraviolet curable compounds that can be incorporated into phase changeink carriers without adversely affecting the viscosity characteristicsof the ink at desired jetting temperatures. In addition, there is a needfor ultraviolet curable compounds that can be incorporated into phasechange ink carriers without adversely affecting the melting point of theink. Further, there is a need for ultraviolet curable phase change inksthat can be used in ink jet printing processes wherein the ink is firstjetted onto an intermediate transfer member and subsequently transferredfrom the transfer member to a final substrate such as paper ortransparency material. Additionally, there is a need for ultravioletcurable phase change inks that can be used in ink jet printing processeswherein the ink is first jetted onto an intermediate transfer member andsubsequently transferred from the transfer member to a final substratesuch as paper or transparency material, wherein the intermediatetransfer member is maintained at a temperature between the jettingtemperature of the ink and the temperature of the final substrate. Aneed also remains for ultraviolet curable compounds that can beincorporated into phase change ink carriers to be used in printingprocesses using heated intermediate transfer members without adverselyaffecting the temperature at which the intermediate transfer member caneffectively transfuse the image thereon to the final substrate. Inaddition, a need remains for curable phase change inks suitable for usein printing processes using heated intermediate transfer members whereinthe ink has desirable viscosity values at the desired jettingtemperatures. Further, a need remains for curable phase change inkssuitable for use in printing processes using heated intermediatetransfer members wherein the ink has desirable viscosity values at thedesired intermediate transfer member temperatures. Additionally, a needremains for curable phase change inks suitable for use in printingprocesses using heated intermediate transfer members wherein the inkgenerates images with reduced showthrough. There is also a need forcurable phase change inks suitable for use in printing processes usingheated intermediate transfer members wherein the ink exhibits improvedtransfer and fusing from the intermediate transfer member to the finalrecording sheet. In addition, there is a need for curable phase changeinks suitable for use in printing processes using heated intermediatetransfer members wherein the ink exhibits improved robustness on thefinal recording sheet. Further, there is a need for phase change inkcarrier components that are compatible with curable components therein.Additionally, there is a need for curable phase change inks thatgenerate images with improved flexibility. A need also remains forcurable phase change inks that generate images with improved toughness.In addition, a need remains for curable phase change inks that exhibitreduced polymerization at ink jetting temperatures. Further, a needremains for curable phase change inks that can be jetted at reducedtemperatures. Additionally, a need also remains for curable phase changeinks that generate images which exhibit reduced shrinkage upon curing.There is also a need for curable phase change inks that generate imageswith desirable gloss characteristics. In addition, there is a need forcomponents in curable phase change ink compositions that enhance thecompatibility and solubility of the other ink components with eachother.

SUMMARY

Disclosed herein is a phase change ink comprising a colorant, aninitiator, and a phase change ink carrier, said carrier comprising (A) afirst isocyanate-derived compound which is the reaction product of amixture comprising (1) an isocyanate; and (2) a component comprising (a)an alcohol having at least one ethylenic unsaturation; (b) an aminehaving at least one ethylenic unsaturation; (c) an acid having at leastone ethylenic unsaturation; or (d) mixtures thereof, (B) a secondisocyanate-derived compound which is the reaction product of (1) adiisocyanate; (2) a monoalcohol having exactly one hydroxyl group andhaving at least one ethylenic unsaturation; and (3) a polyol having twoor more hydroxyl groups, (C) an optional phase change inducingcomponent, said phase change inducing component containing at least onehydroxyl group, said phase change inducing component having a meltingpoint of about 40° C. or higher, and (D) an optional curable viscositymodifying ester, said ink being curable upon exposure to ultravioletradiation.

DETAILED DESCRIPTION

The ink vehicle contains a first isocyanate-derived compound that is thereaction product of a mixture comprising (1) an isocyanate; and (2) acomponent comprising (a) an alcohol having at least one ethylenicunsaturation; (b) an amine having at least one ethylenic unsaturation;(c) an acid having at least one ethylenic unsaturation; or (d) mixturesthereof. These reaction products can include amides, ureas, urethanes,urea/urethanes, amide/urethanes, and the like, as well as mixturesthereof. For example, the reaction products of an alcohol and anisocyanate can include urethanes. The reaction products of an amine andan isocyanate can include ureas. The reaction products of an acid and anisocyanate can include amides. The reaction products of an isocyanateand a mixture of an alcohol and an amine can include urea-urethanes. Thereaction products of an isocyanate and a mixture of an acid and analcohol can include amide-urethanes.

Suitable isocyanates include monomeric, oligomeric, and polymericisocyanates, including (but are not limited to) those of the generalformula R₁—(NCO)_(n) wherein R₁ is (i) an alkyl or alkylene group(including linear and branched, saturated and unsaturated, cyclic andacyclic, and substituted and unsubstituted alkyl and alkylene groups,and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylor alkylene group), in one embodiment with at least about 8 carbonatoms, in another embodiment with at least about 10 carbon atoms, and inyet another embodiment with at least about 12 carbon atoms, and in oneembodiment with no more than about 60 carbon atoms, in anotherembodiment with no more than about 50 carbon atoms, and in yet anotherembodiment with no more than about 40 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (ii) an aryl or arylenegroup (including substituted and unsubstituted aryl and arylene groups,and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the aryl orarylene group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iii) an arylalkyl orarylalkylene group (including substituted and unsubstituted arylalkyland arylalkylene groups, wherein the alkyl portion of the arylalkyl orarylalkylene group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either the aryl or the alkylportion of the arylalkyl or arylalkylene group), in one embodiment withat least about 6 carbon atoms, and in another embodiment with at leastabout 7 carbon atoms, and in one embodiment with no more than about 60carbon atoms, in another embodiment with no more than about 40 carbonatoms, and in yet another embodiment with no more than about 30 carbonatoms, although the number of carbon atoms can be outside of theseranges, or (iv) an alkylaryl or alkylarylene group (includingsubstituted and unsubstituted alkylaryl and alkylarylene groups, whereinthe alkyl portion of the alkylaryl or alkylarylene group can be linearor branched, saturated or unsaturated, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either the aryl or the alkyl portion of the alkylarylor alkylarylene group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 60 carbon atoms, in anotherembodiment with no more than about 40 carbon atoms, and in yet anotherembodiment with no more than about 30 carbon atoms, although the numberof carbon atoms can be outside of these ranges, wherein the substituentson the substituted alkyl, alkylene, aryl, arylene, arylalkyl,arylalkylene, alkylaryl, and alkylarylene groups can be (but are notlimited to) halogen atoms, imine groups, ammonium groups, cyano groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups,ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonylgroups, sulfate groups, sulfonate groups, sulfide groups, sulfoxidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, sulfone groups,acyl groups, acid anhydride groups, azide groups, azo groups, cyanatogroups, isocyanato groups, thiocyanato groups, isothiocyanato groups,carboxylate groups, mixtures thereof, and the like, wherein two or moresubstituents can be joined together to form a ring, and n is an integerrepresenting the number of isocyanate groups, being, for example, 1, 2,3, or the like in the instance of monomeric isocyanates and having nonecessary upper limit in the case of polymeric isocyanates. In onespecific embodiment, the isocyanate is a monoisocyanate, a diisocyanate,or a triisocyanate.

Examples of suitable isocyanates include monoisocyanates, diisocyanates,triisocyanates, copolymers of a diisocyanate, copolymers of atriisocyanate, polyisocyanates (having more than three isocyanatefunctional groups), and the like, as well as mixtures thereof. Examplesof monoisocyanates include n-octadecylisocyanate, of the formulaCH₃—(CH₂)₁₇—NCO;other isomers of octadecylisocyanate; hexadecylisocyanate;octylisocyanate; n-butyl and t-butylisocyanate; cyclohexyl isocyanate;adamantyl isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropylisocyanate; benzylisocyanate; 2-ethylphenylisocyanate;benzoylisocyanate; meta and para-tolylisocyanate; 2-, 3-, or4-nitrophenylisocyanates; 2-ethoxyphenyl isocyanate; 3-methoxyphenylisocyanate; 4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like, as well as mixtures thereof.Examples of diisocyanates include isophorone diisocyanate (IPDI), of theformula

toluene diisocyanate (TDI); diphenylmethane-4,4′-diisocyanate (MDI);hydrogenated diphenylmethane-4,4′-diisocyanate (H12MDI); tetra-methylxylene diisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI), ofthe formulaOCN—(CH₂)₆—NCO;naphthalene-1,5-diisocyanate; 3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate; 4,4′-biphenyldiisocyanate; 2,2,4-trimethylhexamethylenediisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, of theformulae

tetramethylene xylene diisocyanate; 4,4′-methylenebis(2,6-diethylphenylisocyanate); 1,12-diisocyanatododecane;1,5-diisocyanato-2-methylpentane; 1,4-diisocyanatobutane; dimerdiisocyanate and cyclohexylene diisocyanate and its isomers; uretidionedimers of HDI; and the like, as well as mixtures thereof. Examples oftriisocyanates or their equivalents include the trimethylolpropanetrimer of TDI, and the like, isocyanurate trimers of TDI, HDI, IPDI, andthe like, and biuret trimers of TDI, HDI, IPDI, and the like, as well asmixtures thereof. Examples of higher isocyanate functionalities includecopolymers of TDI/HDI, and the like, and MDI oligomers, as well asmixtures thereof.

Examples of suitable acids include any ethylenically unsaturated acid,including (but not limited to) those of the formula R₂—COOH wherein R₂is (i) an alkyl group having at least one ethylenic unsaturation therein(including linear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at leastabout 2 carbon atoms, in another embodiment with at least about 4 carbonatoms, in yet another embodiment with at least about 6 carbon atoms, andin still another embodiment with at least about 10 carbon atoms, and inone embodiment with no more than about 40 carbon atoms, in anotherembodiment with no more than about 30 carbon atoms, in yet anotherembodiment with no more than about 22 carbon atoms, and in still anotherembodiment with no more than about 11 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (ii) an arylalkyl grouphaving at least one ethylenic unsaturation therein (includingsubstituted and unsubstituted arylalkyl groups, wherein the alkylportion of the arylalkyl group can be linear or branched, cyclic oracyclic, and substituted or unsubstituted, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkyl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (iii) an alkylarylgroup having at least one ethylenic unsaturation therein (includingsubstituted and unsubstituted alkylaryl groups, wherein the alkylportion of the alkylaryl group can be linear or branched, cyclic oracyclic, and substituted or unsubstituted, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either the aryl or the alkyl portionof the alkylaryl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, wherein the substituentson the substituted alkyl, arylalkyl, and alkylaryl groups can be (butare not limited to) hydroxy groups, halogen atoms, imine groups,ammonium groups, cyano groups, pyridine groups, pyridinium groups, ethergroups, aldehyde groups, ketone groups, ester groups, amide groups,carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups,sulfonic acid groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, nitrile groups, mercaptogroups, nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, azo groups, cyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.In one specific embodiment, the ethylenically unsaturated acid is amonoacid, a diiacid, or a triacid.

Some specific examples of suitable ethylenically unsaturated acidsinclude 10-undecenoic acid, of the formula

21-docosenoic acid, 6-heptenoic acid, 2,2-dimethyl-4-pentenoic acid,2,2-dimethyl-but-3-enoic acid, acrylic acid, methacrylic acid,3-butenoic acid, 3,7-dimethyl-6-octenoic acid, crotonic acid, 9-decenoicacid, 3-hexenoic acid, 2-methyl-3-butenoic acid, 7-oxo-11-dodecenoicacid, 7-oxo-16-heptadecenoic acid, 6-oxo-15-hexadecenoic acid,7-oxo-8-nonenoic acid, 4-pentenoic acid, and the like, as well asmixtures thereof.

If desired, a mixture of acids including an ethylenically unsaturatedacid and an acid containing no ethylenic unsaturations can be used inthe reaction with the isocyanate. By so doing, the characteristics ofthe product can be further tailored as desired. For example, theethylenically unsaturated acid can impart to the product curability,when in the presence of one or more suitable photoinitiators, uponexposure to ultraviolet radiation, while the acid containing noethylenic unsaturations can impart to the product desirable solubilitycharacteristics.

Examples of suitable acids containing no ethylenic unsaturations include(but are not limited to) those of the formula R₂′—COOH wherein R₂′ is(i) an alkyl group (including linear and branched, cyclic and acyclic,and substituted and unsubstituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least about 7 carbon atoms, in another embodimentwith at least about 10 carbon atoms, in yet another embodiment with atleast about 15 carbon atoms, and in still another embodiment with atleast about 30 carbon atoms, and in one embodiment with no more thanabout 60 carbon atoms, in another embodiment with no more than about 50carbon atoms, and in yet another embodiment with no more than about 40carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (ii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iii) anarylalkyl group (including substituted and unsubstituted arylalkylgroups, wherein the alkyl portion of the arylalkyl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 25carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or (iv) an alkylaryl group (including substituted andunsubstituted alkylaryl groups, wherein the alkyl portion of thealkylaryl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either the aryl or the alkyl portion of the alkylarylgroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, wherein the substituentson the substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be(but are not limited to) hydroxy groups, halogen atoms, imine groups,ammonium groups, cyano groups, pyridine groups, pyridinium groups, ethergroups, aldehyde groups, ketone groups, ester groups, amide groups,carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups,sulfonic acid groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, nitrile groups, mercaptogroups, nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, azo groups, cyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.In one specific embodiment, the acid containing no ethylenicunsaturations is a monoacid, a diiacid, or a triacid.

Specific examples of suitable acids containing no ethylenicunsaturations include, but are not limited to, formic acid, acetic acid,propionic acid, butyric acid (all isomers), valeric acid (all isomers),hexanoic acid (all isomers), heptanoic acid (all isomers), octanoic acid(all isomers), nonanoic acid (all isomers), decanoic acid (all isomers),undecanoic acid (all isomers), dodecanoic acid (all isomers),tridecanoic acid (all isomers), tetradecanoic acid (all isomers),pentadecanoic acid (all isomers), hexadecanoic acid (all isomers),heptadecanoic acid (all isomers), octadecanoic acid (all isomers),nonadecanoic acid (all isomers), eicosanoic acid (all isomers),heneicosanoic acid (all isomers), docosanoic acid (all isomers),cyclohexanecarboxylic acid, cyclopentylacetic acid,cycloheptanecarboxylic acid, 2-norbornaneacetic acid, and the like, aswell as mixtures thereof. Also suitable are mixtures of acids having thestructure CH₃(CH₂)_(n)COOH wherein n has an average value of from about16 to about 50, commercially available as, for example, UNICID® 350,UNICID® 425, UNICID® 550, and UNICID® 700 with Mn values of about 390,475, 565, and 720, respectively. Other suitable acids having noethylenic unsaturations include those of the general formulaCH₃(CH₂)_(n)COOH, such as tetracosanoic or lignoceric acid (n=22),hexacosanoic or cerotic acid (n=24), heptacosanoic or carboceric acid(n=25), octacosanoic or montanic acid (n=26), triacontanoic or melissicacid (n=28), dotriacontanoic or lacceroic acid (n=30), tritriacontanoicor ceromelissic or psyllic acid (n=31), tetratriacontanoic or geddicacid (n=32), pentatriacontanoic or ceroplastic acid (n=33), isomersthereof, and the like. Also suitable is PRIPOL® 1009, a C-36 dimer acidmixture including isomers of the formula

as well as other branched isomers, which may include unsaturations andcyclic groups, commercially available from Uniqema, New Castle, Del.;further information on C₃₆ dimer acids of this type is disclosed in, forexample, “Dimer Acids,” Kirk-Othmer Encyclopedia of Chemical Technology,Vol. 8, 4^(th) Ed. (1992), pp. 223 to 237, the disclosure of which istotally incorporated herein by reference. Mixtures of two or more of anyof these acids are also suitable.

Examples of suitable alcohols include any ethylenically unsaturatedalcohol, including (but not limited to) those of the formula R₃—OHwherein R₃ is (i) an alkyl group having at least one ethylenicunsaturation therein (including linear and branched, cyclic and acyclic,and substituted and unsubstituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least about 5 carbon atoms, in another embodimentwith at least about 8 carbon atoms, and in yet another embodiment withat least about 12 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 30carbon atoms, and in yet another embodiment with no more than about 15carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (ii) an arylalkyl group having at least one ethylenicunsaturation therein (including substituted and unsubstituted arylalkylgroups, wherein the alkyl portion of the arylalkyl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 25carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or (iii) an alkylaryl group having at least one ethylenicunsaturation therein (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the alkylaryl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 25carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, wherein the substituents on the substituted alkyl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, amine groups, halogen atoms, imine groups, ammonium groups,cyano groups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, thiocyanato groups,isothiocyanato groups, carboxylate groups, carboxylic acid groups,urethane groups, urea groups, mixtures thereof, and the like, whereintwo or more substituents can be joined together to form a ring. In onespecific embodiment, the ethylenically unsaturated alcohol is amonoalcohol, a diol, or a triol.

Some specific examples of suitable ethylenically unsaturated alcoholsinclude 1,4-butanediol vinyl ether, of the formulaHO—(CH₂)₄—O—CH═CH₂available from Sigma-Aldrich, Milwaukee, Wis., 2-allyloxyethanol, of theformulaHO—(CH₂)₂—O—CH₂—CH═CH₂1,4-cyclohexanedimethanol vinyl ether (cis and trans isomers), of theformula

ethylene glycol vinyl ether, of the formula

di(ethylene glycol) vinyl ether, of the formula

TONE M-100, commercially available from Dow Chemical Company, Midland,Mich., believed to be of the formula

compounds of the formula

such as CD572, wherein n=10, commercially available from SartomerCompany, Exton, Pa., and the like, as well as mixtures thereof.

If desired, a mixture of alcohols including an ethylenically unsaturatedalcohol and an alcohol containing no ethylenic unsaturations can be usedin the reaction with the isocyanate. By so doing, the characteristics ofthe product can be further tailored as desired. For example, theethylenically unsaturated alcohol can impart to the product curability,when in the presence of one or more suitable photoinitiators, uponexposure to ultraviolet radiation, while the alcohol containing noethylenic unsaturations can impart to the product desirable solubilitycharacteristics.

Examples of suitable alcohols containing no ethylenic unsaturationsinclude (but are not limited to) those of the formula R₃′—OH wherein R₃′is (i) an alkyl group (including linear and branched, cyclic andacyclic, and substituted and unsubstituted alkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the alkyl group), in oneembodiment with at least about 1 carbon atom, in another embodiment withat least about 6 carbon atoms, in yet another embodiment with at leastabout 10 carbon atoms, and in still another embodiment at least about 16carbon atoms, and in one embodiment with no more than about 60 carbonatoms, in another embodiment with no more than about 50 carbon atoms,and in yet another embodiment with no more than about 40 carbon atoms,although the number of carbon atoms can be outside of these ranges, (ii)an aryl group (including substituted and unsubstituted aryl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the arylgroup), in one embodiment with at least about 5 carbon atoms, and inanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iii) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, wherein thealkyl portion of the arylalkyl group can be linear or branched, cyclicor acyclic, and substituted or unsubstituted, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkyl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (iv) an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, whereinthe alkyl portion of the alkylaryl group can be linear or branched,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either the aryl or the alkylportion of the alkylaryl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, wherein thesubstituents on the substituted alkyl, aryl, arylalkyl, and alkylarylgroups can be (but are not limited to) hydroxy groups, amine groups,halogen atoms, imine groups, ammonium groups, cyano groups, pyridinegroups, pyridinium groups, ether groups, aldehyde groups, ketone groups,ester groups, amide groups, carbonyl groups, thiocarbonyl groups,sulfate groups, sulfonate groups, sulfonic acid groups, sulfide groups,sulfoxide groups, phosphine groups, phosphonium groups, phosphategroups, nitrile groups, mercapto groups, nitro groups, nitroso groups,sulfone groups, acyl groups, acid anhydride groups, azide groups, azogroups, cyanato groups, thiocyanato groups, isothiocyanato groups,carboxylate groups, carboxylic acid groups, urethane groups, ureagroups, mixtures thereof, and the like, wherein two or more substituentscan be joined together to form a ring. In one specific embodiment, thealcohol containing no ethylenic unsaturations is a monoalcohol, a diol,or a triol.

Specific examples of suitable alcohols containing no ethylenicunsaturations include aliphatic alcohols, including linear, branched,and cyclic aliphatic alcohols, such as methanol, ethanol, propanol (allisomers), butanol (all isomers), pentanol (all isomers), hexanol (allisomers), heptanol (all isomers), octanol (all isomers), nonanol (allisomers), decanol (all isomers), undecanol (all isomers), dodecanol (allisomers), tridecanol (all isomers), tetradecanol (all isomers),pentadecanol (all isomers), hexadecanol (all isomers), heptadecanol (allisomers), octadecanol (all isomers), nonadecanol (all isomers),eicosanol (C₂₀H₄₁OH; all isomers), heneicosanol (C₂₁H₄₃OH; all isomers),docosanol (C₂₂H₄₅OH; all isomers), and the like,3-cyclohexyl-1-propanol, 2-cyclohexyl-1-ethanol, cyclohexylmethanol,cyclohexanol, 4-methyl cyclohexanol, 4-ethylcyclohexanol,4-t-butylcyclohexanol, and the like; aliphatic/aromatic alcohols, suchas benzyl alcohol, octyl, nonyl, and dodecylphenol alkoxylates of octyl,nonyl, and dodecylphenol, and alkoxyphenol; aromatic alcohols such asphenol, naphthol, and the like, and their derivatives; fused ringalcohols, such as rosin alcohols, cholesterol, vitamin E, dimer diol, ofthe formula HO—C₃₆H_(64+n)—OH wherein n is an integer of 0, 1, 2, 3, 4,5, 6, 7, 8, 9, or 10, including isomers of the formula

as well as unsaturated and cyclized derivatives, and the like,commercially available from Uniqema Chemicals, New Castle, Del., Guerbetalcohols, which are 2,2-dialkyl-1-ethanols, including (but not limitedto) those of the general formula

wherein m+n is greater than or equal to 10, in one embodiment being fromabout 16 to about 36, commercially available from Tomah Chemicals andJarchem Industries Inc., Newark, N.J., the UNILIN® products availablefrom Petrolite Chemicals, including but not limited to those of theformula CH₃(CH₂)_(a)OH wherein a is an integer of from about 25 to about50, branched and straight chain alcohols available from Sigma-Aldrich,Milwaukee, Wis., including but not limited to those of the formulaC_(b)H_(2b)OH wherein b is an integer of from about 9 to about 24, andother alcohols, such as N,N-dimethyl-N-ethanolamine,stearamide-monoethanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, ethylene glycol, diethylene glycol, triethylene glycol,dimethylolpropionic acid, sucrose, polytetramethylene glycol,polypropylene glycol, polyester polyols, polyethylene glycol,pentaerythritol, triethanolamine, glycerin, 1,6-hexanediol,N-methyl-N,N-diethanol amine, trimethylol propane,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and the like, aswell as mixtures thereof.

Examples of suitable amines include any ethylenically unsaturatedprimary or secondary amine, including (but not limited to) those of theformula R₄—NHR₅ wherein R₄ is (i) an alkyl group having at least oneethylenic unsaturation therein (including linear and branched, cyclicand acyclic, and substituted and unsubstituted alkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the alkyl group), in oneembodiment with at least about 5 carbon atoms, in another embodimentwith at least about 8 carbon atoms, and in yet another embodiment withat least about 12 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 30carbon atoms, and in yet another embodiment with no more than about 15carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (ii) an arylalkyl group having at least one ethylenicunsaturation therein (including substituted and unsubstituted arylalkylgroups, wherein the alkyl portion of the arylalkyl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 25carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or (iii) an alkylaryl group having at least one ethylenicunsaturation therein (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the alkylaryl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 25carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, and wherein R₅ can be (i) a hydrogen atom, (ii) an alkylgroup (including linear and branched, saturated and unsaturated, cyclicand acyclic, and substituted and unsubstituted alkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, and in one embodiment with nomore than about 50 carbon atoms, in another embodiment with no more thanabout 30 carbon atoms, and in yet another embodiment with no more thanabout 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 30 carbon atoms, and in yetanother embodiment with no more than about 15 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iv) an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, whereinthe alkyl portion of the arylalkyl group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either the aryl or the alkyl portion of the arylalkyl group),in one embodiment with at least about 6 carbon atoms, and in anotherembodiment with at least about 7 carbon atoms, and in one embodimentwith no more than about 50 carbon atoms, in another embodiment with nomore than about 30 carbon atoms, and in yet another embodiment with nomore than about 15 carbon atoms, although the number of carbon atoms canbe outside of these ranges, or (v) an alkylaryl group (includingsubstituted and unsubstituted alkylaryl groups, wherein the alkylportion of the alkylaryl group can be linear or branched, saturated orunsaturated, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the alkylaryl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 30carbon atoms, and in yet another embodiment with no more than about 15carbon atoms, although the number of carbon atoms can be outside ofthese ranges, wherein the substituents on the substituted alkyl, aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, amine groups, halogen atoms, imine groups, ammonium groups,cyano groups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, thiocyanato groups,isothiocyanato groups, carboxylate groups, urethane groups, urea groups,mixtures thereof, and the like, wherein two or more substituents can bejoined together to form a ring. In one specific embodiment, theethylenically unsaturated amine is a monoamine, a diamine, or atriamine.

Examples of suitable amines include 2(1-cyclohexenyl)ethylamine,commercially available from Sigma-Aldrich Chemical Co., Milwaukee, Wis.,of the formula

N-ethyl-2-methylallylamine, commercially available from Sigma-AldrichChemical Co., Milwaukee, Wis., of the formula

monoethanolamine vinyl ether, commercially available from Alash Ltd.,Temirtau, Kazakhstan, of the formula

and the like.

If desired, a mixture of amines including an ethylenically unsaturatedamine and an amine containing no ethylenic unsaturations can be used inthe reaction with the isocyanate. By so doing, the characteristics ofthe product can be further tailored as desired. For example, theethylenically unsaturated amine can impart to the product curability,when in the presence of one or more suitable photoinitiators, uponexposure to ultraviolet radiation, while the amine containing noethylenic unsaturations can impart to the product desirable solubilitycharacteristics.

Examples of suitable amines containing no ethylenic unsaturationsinclude (but are not limited to) those of the formula R₄′—NHR₅′ whereinR₄′ is (i) an alkyl group (including linear and branched, cyclic andacyclic, and substituted and unsubstituted alkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, in another embodiment with atleast about 6 carbon atoms, in yet another embodiment with at leastabout 10 carbon atoms, and in still another embodiment with at leastabout 16 carbon atoms, and in one embodiment with no more than about 60carbon atoms, in another embodiment with no more than about 50 carbonatoms, and in yet another embodiment with no more than about 40 carbonatoms, although the number of carbon atoms can be outside of theseranges, (ii) an aryl group (including substituted and unsubstituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 40 carbon atoms, and in yet anotherembodiment with no more than about 30 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iii) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, wherein thealkyl portion of the arylalkyl group can be linear or branched, cyclicor acyclic, and substituted or unsubstituted, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkyl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 40 carbon atoms, and in yet anotherembodiment with no more than about 30 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (iv) an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, whereinthe alkyl portion of the alkylaryl group can be linear or branched,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either the aryl or the alkylportion of the alkylaryl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 40 carbon atoms, and in yetanother embodiment with no more than about 30 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, and wherein R₅′can be (i) a hydrogen atom, (ii) an alkyl group (including linear andbranched, saturated and unsaturated, cyclic and acyclic, and substitutedand unsubstituted alkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in the alkyl group), in one embodiment with atleast 1 carbon atom, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 40 carbonatoms, and in yet another embodiment with no more than about 30 carbonatoms, although the number of carbon atoms can be outside of theseranges, (iii) an aryl group (including substituted and unsubstitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 40 carbon atoms, and in yet anotherembodiment with no more than about 30 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iv) an arylalkyl group(including substituted and unsubstituted arylalkyl groups, wherein thealkyl portion of the arylalkyl group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either the aryl or the alkyl portion of the arylalkyl group),in one embodiment with at least about 6 carbon atoms, and in anotherembodiment with at least about 7 carbon atoms, and in one embodimentwith no more than about 50 carbon atoms, in another embodiment with nomore than about 40 carbon atoms, and in yet another embodiment with nomore than about 30 carbon atoms, although the number of carbon atoms canbe outside of these ranges, or (v) an alkylaryl group (includingsubstituted and unsubstituted alkylaryl groups, wherein the alkylportion of the alkylaryl group can be linear or branched, saturated orunsaturated, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the alkylaryl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 40carbon atoms, and in yet another embodiment with no more than about 30carbon atoms, although the number of carbon atoms can be outside ofthese ranges, wherein the substituents on the substituted alkyl, aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, amine groups, halogen atoms, imine groups, ammonium groups,cyano groups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, thiocyanato groups,isothiocyanato groups, carboxylate groups, urethane groups, urea groups,mixtures thereof, and the like, wherein two or more substituents can bejoined together to form a ring. In one specific embodiment, the aminecontaining no ethylenic unsaturations is a monoamine, a diamine, or atriamine.

Specific examples of suitable amines containing no ethylenicunsaturations include aliphatic primary and secondary amines, includinglinear, branched, and cyclic aliphatic amines, such as methyl amine,ethyl amine, propyl amine (all isomers), butyl amine (all isomers),pentyl amine (all isomers), hexyl amine (all isomers), heptyl amine (allisomers), octyl amine (all isomers), nonyl amine (all isomers), decylamine (all isomers), undecyl amine (all isomers); dodecyl amine (allisomers), tridecyl amine (all isomers), tetradecyl amine (all isomers),pentadecyl amine (all isomers), hexadecyl amine (all isomers),heptadecyl amine (all isomers), octadecyl amine (all isomers), nonadecylamine (all isomers), eicosyl amine (C₂₀H₄₁NH; all isomers), heneicosylamine (C₂₁H₄₃NH; all isomers), docosyl amine (C₂₂H₄₅NH; all isomers),dimethyl amine, diethyl amine, dipropyl amine (all isomers), dibutylamine (all isomers), dipentyl amine (all isomers), dihexyl amine (allisomers), diheptyl amine (all isomers), dioctyl amine (all isomers),dinonylamine (all isomers), didecyl amine (all isomers), diundecyl amine(all isomers), didodecyl amine (all isomers), ditridecyl amine (allisomers), ditetradecyl amine (all isomers), dipentadecyl amine (allisomers), dihexadecyl amine (all isomers), diheptadecyl amine (allisomers), dioctadecyl amine (all isomers), cyclohexyl amine,dicyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine, piperidine,pyrrolidine, and the like; an aliphatic/aromatic amine, such as benzylamine or analogues with longer or additional alkyl chains; aromaticamines, such as aniline, anisidine, and the like; fused ring amines,such as rosin amine, tetrahydroabietyl amine, and the like; andmiscellaneous amines, such as adamantyl amine, isonipecotamide,polyoxyalkylenemonoamines, such as M-series JEFFAMINES® availablecommercially from Huntsman Chemical Company of Austin, Tex.;3,3′-diamino-N-methyidipropylamine, and the like. Small amounts (on amolar basis) of polyamines can also be incorporated into the reactionmixture to produce oligomeric species in the resins if so desired.

Additionally, hydroxyl/amino containing compounds can be employed (withdi- and higher functionality isocyanates taking advantage of thedifference in reactivity of the amine over the hydroxyl group, or withmonoisocyanates reacting with the amine preferentially or with both theamine and the hydroxyl groups). Examples of these compounds includeethanolamine, diethanolamine, and the like.

Examples of compounds that can be prepared include (but are not limitedto) urethanes of the formula

wherein n represents the number of repeat urethane functional groups andis at least 1 (for example, 1 in the instance of a reaction between amonoisocyanate and a monoalcohol, 2 in the instance of a reactionbetween a diisocyanate and a monoalcohol, 3, 4, 5, 6, and the like, withn having no necessary upper limit), ureas of the formula

wherein m represents the number of repeat urea functional groups and isat least 1 (for example, 1 in the instance of a reaction between amonoisocyanate and a monoamine, 2 in the instance of a reaction betweena diisocyanate and a monoamine, 3, 4, 5, 6, and the like, with n havingno necessary upper limit), amides of the formula

wherein p represents the number of repeat amide functional groups and isat least 1 (for example, 1 in the instance of a reaction between amonoisocyanate and a monoacid, 2 in the instance of a reaction between adiisocyanate and a monoacid, 3, 4, 5, 6, and the like, with p having nonecessary upper limit), urethane-ureas of the formula

wherein n and m are as previously defined, urethane-amides of theformula

wherein n and m are as previously defined, urethanes of the formula

wherein n is as previously defined and a represents the number of repeaturethane functional groups having no ethylenic unsaturations therein,ureas of the formula

wherein m is as previously defined and b represents the number of repeaturea functional groups having no ethylenic unsaturations therein, amidesof the formula

wherein p is as previously defined and c represents the number of repeatamide functional groups having no ethylenic unsaturations therein,urethane-ureas of the formula

wherein a and m are as previously defined, urethane-ureas of the formula

wherein b and n are as previously defined, urethane-ureas of the formula

wherein a, n, and m are as previously defined, urethane-ureas of theformula

wherein a, b, and n are as previously defined, urethane-ureas of theformula

wherein b, n, and m are as previously defined, urethane-ureas of theformula

wherein a, b, and m are as previously defined, urethane-ureas of theformula

wherein a, b, m, and n are as previously defined, urethane-amides of theformula

wherein n and c are as previously defined, urethane-amides of theformula

wherein a and p are as previously defined, urethane-amides of theformula

wherein n, p, and c are as previously defined, urethane-amides of theformula

wherein a, p, and c are as previously defined, urethane-amides of theformula

wherein a, p, and n are as previously defined, urethane-amides of theformula

wherein a, c, and n are as previously defined, urethane-amides of theformula

wherein a, c, p, and n are as previously defined, and the like.

Any suitable reaction conditions for making urethane, urea, orurethane/urea compounds by condensing alcohols and/or amines withisocyanates can be used to prepare the urethane, urea, urea-urethane, oramide-urethane first isocyanate -derived compounds. Typically (althoughnot necessarily), the reaction is carried out at elevated temperatures(for example, from about 45 to about 160° C.) in the presence of anoptional reaction catalyst, such as dibutyl tin dilaurate, bismuthtris-neodecanoate, cobalt benzoate, lithium acetate, stannous octoate,triethylamine, or the like. In a specific embodiment, the reactionconditions are conducted in an inert atmosphere, such as argon ornitrogen gas or other suitable gases, to prevent oxidizing or yellowingof the reaction products and to prevent undesirable side reactions. Thereaction can employ an inert solvent, such as toluene or the like, orcan be performed neat (i.e., without a solvent). The mole ratio ofreactants is adjusted so that the isocyanate functionalities arecompletely consumed in the reaction with a slight molar excess ofalcohol and/or amine typically remaining. The reactants can be addedtogether in any order and/or added to the reaction as physical mixtures.If desired, reaction conditions and the order of the addition ofreactants can be controlled for several reasons, such as to provide acontrolled exothermic reaction, to tailor the distribution of moleculeswhen reacting a diisocyanate with a mixture of an alcohol and an amine,or the like. When doing these adjustments, the different reactivities toisocyanates of alcohols versus amines can be employed, as well as thedifferent reactivities of the two separate isocyanate groups ondiisocyanates such as isophorone diisocyanate. See, for example, J. H.Saunders and K. C. Frisch's “Polyurethanes Part I, Chemistry” publishedby Interscience of New York, N.Y. in 1962 and Olin Chemicals' LUXATE® IMisophorone diisocyanate technical product information sheet, thedisclosures of each of which are totally incorporated herein byreference, which provide further explanation of this chemistry. By sotailoring the distribution of molecules, one can control the finishedproduct to have a controlled viscosity that is designed for a specificapplication, have a controlled glass transition temperature and/ormelting point, have consistent properties from batch to batch, or thelike.

The reaction can be carried out either neat or, optionally, in thepresence of a solvent. When present, any desired or effective solventcan be used. Examples of suitable solvents include xylene, toluene,benzene, chlorobenzene, nitrobenzene, dichlorobenzene, N-methylpyrrolidinone, dimethyl formamide, dimethyl sulfoxide, sulfolane,hexane, tetrahydrofuran, and the like, as well as mixtures thereof.

Reactions wherein isocyanates are reacted with alcohols, amines, andacids to form urethanes, ureas, and amides are also disclosed in, forexample, U.S. application Ser. No. 10/260,146 (U.S. Publication20040077887), U.S. Pat. No. 6,821,327, U.S. application Ser. Nos.10/260,379 (U.S. Publication 20040082801), 10/369,981 (U.S. Publication20040167249), 10/918,053, and 10/918,619, the disclosures of each ofwhich are totally incorporated herein by reference.

Compounds as disclosed herein can be used as components in phase changeink carriers. The phase change carrier composition is typically designedfor use in either a direct printing mode or an indirect or offsetprinting transfer system.

In the direct printing mode, the phase change carrier composition in oneembodiment contains one or more materials that enable the phase changeink (1) to be applied in a thin film of uniform thickness on the finalrecording substrate (such as paper, transparency material, and the like)when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

In an offset printing transfer or indirect printing mode, the phasechange carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958 thedisclosure of which is totally incorporated herein by reference.

The first isocyanate-based curable compound is present in the phasechange ink carrier in any desired or effective amount, in one embodimentat least about 0.1 percent by weight of the carrier, in anotherembodiment at least about 1 percent by weight of the carrier, and in yetanother embodiment at least about 10 percent by weight of the carrier,and in one embodiment no more than about 99 percent by weight of thecarrier, in another embodiment no more than about 90 percent by weightof the carrier, and in yet another embodiment no more than about 80percent by weight of the carrier, although the amount can be outside ofthese ranges.

The phase change carrier composition ink further contains a secondisocyanate-derived compound. In one specific embodiment, this compoundis the reaction product of (1) a diisocyanate; (2) a monoalcohol havingexactly one hydroxyl group and having at least one ethylenicunsaturation; and (3) a polyol having two or more hydroxyl groups.

The isocyanate can be as described hereinabove of the formula R₁—(NCO)₂.Suitable specific examples of diisocyanates are listed hereinabove.

Similarly, the monoalcohol having at least one ethylenic unsaturationcan be as described hereinabove of the formula R₃—OH. The monoalcoholhas no more than one hydroxyl group and has no amino or carboxylic acidgroups thereon. Suitable specific examples of monoalcohols are listedhereinabove.

In one specific embodiment, the monoalcohol is a vinyl ether, of thegeneral formulaHO—R₃₃—OCH═CH₂wherein R₃₃ is (i) an alkyl group (including linear and branched,saturated and unsaturated, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at leastabout 3 carbon atom, in another embodiment with at least about 6 carbonatoms, in yet another embodiment with at least about 10 carbon atoms,and in one embodiment with no more than about 48 carbon atoms, inanother embodiment with no more than about 28 carbon atoms, and in yetanother embodiment with no more than about 13 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (ii) an arylgroup (including substituted and unsubstituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the aryl group), in oneembodiment with at least about 5 carbon atoms, and in another embodimentwith at least about 6 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 40 carbon atoms, and in yet another embodiment with no more thanabout 30 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an arylalkyl group (including substitutedand unsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either the aryl or the alkylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 48 carbon atoms, inanother embodiment with no more than about 23 carbon atoms, and in yetanother embodiment with no more than about 10 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, or (iv) analkylaryl group (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, saturated or unsaturated, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either the aryl or the alkyl portion of the alkylarylgroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 48 carbon atoms, in anotherembodiment with no more than about 23 carbon atoms, and in yet anotherembodiment with no more than about 10 carbon atoms, although the numberof carbon atoms can be outside of these ranges, wherein the substituentson the substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be(but are not limited to) halogen atoms, imine groups, ammonium groups,cyano groups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, thiocyanato groups,isothiocyanato groups, urethane groups, urea groups, mixtures thereof,and the like, wherein two or more substituents can be joined together toform a ring.

The polyol is of the general formula R₇(OH)_(z) wherein z is an integerrepresenting the number of hydroxyl groups and is at least about 2 andhas no necessary upper limit, particularly when R₇ is an oligomeric orpolymeric group, and R₇ is (i) an alkyl group (including linear andbranched, saturated and unsaturated, cyclic and acyclic, and substitutedand unsubstituted alkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in the alkyl group), in one embodiment with atleast about 2 carbon atoms, in another embodiment with at least about 4carbon atoms, in yet another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 100 carbon atoms,in another embodiment with no more than about 75 carbon atoms, and inyet another embodiment with no more than about 50 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, (ii) an arylgroup (including substituted and unsubstituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the aryl group), in oneembodiment with at least about 5 carbon atoms, and in another embodimentwith at least about 6 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 40 carbon atoms, and in yet another embodiment with no more thanabout 30 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an arylalkyl group (including substitutedand unsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either the aryl or the alkylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 40 carbon atoms, and in yetanother embodiment with no more than about 30 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iv) analkylaryle group (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, saturated or unsaturated, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either the aryl or the alkyl portion of the alkylarylgroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 40 carbon atoms, and in yet anotherembodiment with no more than about 30 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (v) an oligomeric orpolymeric group, wherein the substituents on the substituted alkyl,aryl, arylalkyl, and alkylaryl groups can be (but are not limited to)hydroxy groups, halogen atoms, imine groups, ammonium groups, cyanogroups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfide groups,sulfoxide groups, phosphine groups, phosphonium groups, phosphategroups, nitrile groups, mercapto groups, nitro groups, nitroso groups,sulfone groups, acyl groups, acid anhydride groups, azide groups, azogroups, cyanato groups, thiocyanato groups, isothiocyanato groups,carboxylate groups, mixtures thereof, and the like, wherein two or moresubstituents can be joined together to form a ring.

Specific examples of suitable polyols include trimethylolpropane, of theformula

di(trimethylolpropane), of the formula

1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,12-dodecanediol, 1,13 tridecanediol, 1,14-tetradecanediol,1,15-pentadecanediol, 1,16 hexandecanediol, 1,17-heptadecanediol,1,18-octadecanediol, 1,19 nonadecanediol, 1,20-eicosanediol,1,22-docosanediol, 1,25-pentacosanediol, trimethylolethane,pentaerythritol, pentaerythritol ethoxylate, pentaerythritolpropoxylate, polypropylene glycol, polyethylene glycol, polyethyleneadipate, poly(tetramethylene ether)glycol, glycerol, and the like, aswell as mixtures thereof. Examples of aryl polyhydroxy materials aredisclosed in, for example, U.S. application Ser. No. 10/721,140 and U.S.application Ser. No. 10/722,326, the disclosures of each of which aretotally incorporated herein by reference.

The second isocyanate-derived compound can be prepared by any desired oreffective method. For example, these compounds can be prepared by firstreacting the diisocyanate and the monoalcohol having at least oneethylenic unsaturation in approximately equimolar amounts at elevatedtemperatures, optionally in the presence of a catalyst. Thereafter, theresulting product can be cooled to about room temperature and reactedwith about z moles of product per every 1 mole of a polyol of theformula R₇(OH)_(z) before returning the reaction mixture to an elevatedtemperature. The reaction proceeds as follows (illustrated for theexample of a triol):

The unsaturated monoalcohol and the diisocyanate are present in relativeamounts of at least about 0.8 mole of unsaturated monoalcohol per everyone mole of diisocyanate, and of no more than about 1.2 moles ofunsaturated monoalcohol per every one mole of diisocyanate; in anotherembodiment the unsaturated monoalcohol is present in an amount of nomore than about 1 mole of unsaturated monoalcohol per every one mole ofdiisocyanate.

Examples of suitable catalysts include (but are not limited to) Lewisacid catalysts such as dibutyl tin dilaurate, bismuth tris-neodecanoate,cobalt benzoate, lithium acetate, stannous octoate, triethylamine,ferric chloride, aluminum trichloride, boron trichloride, borontrifluoride, titanium tetrachloride, tin tetrachloride, and the like.The catalyst, when present, is present in any desired or effectiveamount, in one embodiment at least about 0.2 mole percent, in anotherembodiment at least about 0.5 mole percent, and in yet anotherembodiment at least about 1 mole percent, and in one embodiment no morethan about 10 mole percent, in another embodiment no more than about 7.5mole percent, and in yet another embodiment no more than about 5 molepercent, based on the amount of diisocyanate, although the amount can beoutside of these ranges.

Examples of suitable solvents for the first part of the reaction include(but are not limited to) toluene, hexane, heptane, methylene chloride,tetrahydrofuran, diethyl ether, ethyl acetate, methyl ethyl ketone, andthe like, as well as mixtures thereof. When present, the solvent ispresent in any desired amount, in one embodiment at least about 1milliliters per millimole of diisocyanate, in another embodiment atleast about 1.5 milliliters per millimole of diisocyanate, in anotherembodiment at least about 2 milliliters per millimole of diisocyanate,and in one embodiment no more than about 30 milliliters per millimole ofdiisocyanate, in another embodiment no more than about 25 millilitersper millimole of diisocyanate, and in yet another embodiment no morethan about 20 milliliters per millimole of diisocyanate, although theamount can be outside of these ranges.

The isocyanate and the alcohol are heated to any desired or effectivetemperature, in one embodiment at least about 25° C., in anotherembodiment at least about 40° C., and in yet another embodiment at leastabout 50° C., and in one embodiment no more than about 125° C., inanother embodiment no more than about 100° C., and in yet anotherembodiment no more than about 75° C., although the amounts can beoutside of these ranges.

The isocyanate and the alcohol are heated for any desired or effectiveperiod of time, in one embodiment at least about 5 minutes, in anotherembodiment at least about 10 minutes, and in yet another embodiment atleast about 15 minutes, and in one embodiment no more than about 80minutes, in another embodiment no more than about 40 minutes, and in yetanother embodiment no more than about 30 minutes, although the time canbe outside of these ranges.

Subsequent to the reaction between the diisocyanate and the monoalcohol,the first reaction product need not be recovered; the reaction mixturecan be cooled to room temperature and the polyol can be added to thereaction mixture, along with additional solvent if desired to completethe reaction.

The first reaction product and the polyol R₇(OH)_(z) are present in anydesired or effective relative amounts, in one embodiment at least about1/z moles of first reaction product per every one mole of polyol, inanother embodiment at least about 1.2/z moles of first reaction productper every one mole of polyol, and in yet another embodiment at leastabout 1.4/z moles of first reaction product per every one mole ofpolyol, and in one embodiment no more than about 2/z moles of firstreaction product per every one mole of polyol, in another embodiment nomore than about 1.9/z moles of first reaction product per every one moleof polyol, and in yet another embodiment no more than about 1.8/z molesof first reaction product per every one mole of polyol, although therelative amounts can be outside of these ranges.

The first reaction product and the polyol are allowed to react at anydesired or effective temperature, in one embodiment at least about 25°C., in another embodiment at least about 40° C., and in yet anotherembodiment at least about 50° C., and in one embodiment no more thanabout 125° C., in another embodiment no more than about 100° C., and inyet another embodiment no more than about 75° C., although thetemperature can be outside of these ranges.

The first reaction product and the polyol are allowed to react for anydesired or effective period of time, in one embodiment at least about0.5 hour, in another embodiment at least about 2 hours, and in yetanother embodiment at least about 4 hours, and in one embodiment no morethan about 24 hours, in another embodiment no more than about 20 hours,and in yet another embodiment no more than about 15 hours, although thetime can be outside of these ranges.

Thereafter, the product can be recovered by removing the solvent invacuo and purified, for example, by trituration with a minimum amount ofa non-solvent, such as hexane.

Specific examples of suitable second isocyanate-derived compoundsinclude the reaction product of 1,6-diisocyanohexane, 1,4-butanediolvinyl ether, and trimethylolpropane, of the formula

the reaction product of trimethyl-1,6-diisocyanatohexane (mixture of2,2,4- and 2,4,4-isomers), 1,4-butanediol vinyl ether, andtrimethylolpropane, of the formula

believed to have many different isomers, wherein each of the threebranches has four possibilities: (1) R₁, R₂, and R₅=CH₃; R₃, R₄, R₆, R₇,and R₈=H; (2) R₁, R₅, and R₆=CH₃; R₂, R₃, R₄, R₇, and R₈=H; (3) R₃, R₇,and R₈=CH₃; R₁, R₂, R₄, R₅, and R₆=H; (4) R₃, R₄, and R₇=CH₃; R₁, R₂,R₅, R₆, and R₈=H; (5) R₉, R₁₀, and R₁₃=CH₃; R₁₁, R₁₂, R₁₄, R₁₅, andR₁₆=H; (6) R₉, R₁₃, and R₁₄=CH₃; R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆=H; (7) R₁₁,R₁₅, and R₁₆=CH₃; R₉, R₁₀, R₁₂, R₁₃, and R₁₄=H; (8) R₁₁, R₁₂, andR₁₅=CH₃; R₉, R₁₀, R₁₃, R₁₄, and R₁₆=H; (9) R₁₇, R₁₈, and R₂₁=CH₃; R₁₉,R₂₀, R₂₂, R₂₃, and R₂₄=H; (10) R₁₇, R₂₁, and R₂₂=CH₃; R₁₈, R₁₉, R₂₀,R₂₃, and R₂₄=H; (11) R₁₉, R₂₃, and R₂₄=CH₃; R₁₇, R₁₈, R₂₀, R₂₁, andR₂₂=H; (12) R₁₉, R₂₀, and R₂₃=CH₃; R₁₇, R₁₈, R₂₁, R₂₂, and R₂₄=H; thereaction product of 1,4-butanediol vinyl ether, anddi(trimethylolpropane), which includes isomers of the formula

as well as other urethane products, the reaction product oftrimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers),1,4-butanediol vinyl ether, and di(trimethylolpropane), of the formula

believed to have many different isomers, wherein each of the threebranches has four possibilities: (1) R₁, R₂, and R₅=CH₃; R₃, R₄, R₆, R₇,and R₈=H; (2) R₁, R₅, and R₆=CH₃; R₂, R₃, R₄, R₇, and R₈=H; (3) R₃, R₇,and R₈=CH₃; R₁, R₂, R₄, R₅, and R₆=H; (4) R₃, R₄, and R₇=CH₃; R₁, R₂,R₅, R₆, and R₈=H; (5) R₉, R₁₀, and R₁₃=CH₃; R₁₁, R₁₂, R₁₄, R₁₅, andR₁₆=H; (6) R₉, R₁₃, and R₁₄=CH₃; R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆=H; (7) R₁₁,R₁₅, and R₁₆=CH₃; R₉, R₁₀, R₁₂, R₁₃, and R₁₄=H; (8) R₁₁, R₁₂, andR₁₅=CH₃; R₉, R₁₀, R₁₃, R₁₄, and R₁₆=H; (9) R₁′, R₂′, and R₅′=CH₃; R₃′,R₄′, R₆′, R₇′, and R₈′=H; (10) R₁′, R₅′, and R₆′=CH₃; R₂′, R₃′, R₄′,R₇′, and R₈′=H; (11) R₃′, R₇′, and R₈′=CH₃; R₁′, R₂′, R₄′, R₅′, andR₆′=H; (12) R₃′, R₄′, and R₇′=CH₃; R₁′, R₂′, R₅′, R₆′, and R₈′=H; (13)R₉′, R₁₀′, and R₁₃′=CH₃; R₁₁′, R₁₂′, R₁₄′, R₁₅′, and R₁₆′=H; (14) R₉′,R₁₃′, and R₁₄′=CH₃; R₁₀′, R₁₁′, R₁₂′, R₁₅′, and R₁₆′=H; (15) R₁₁′, R₁₅′,and R₁₆′=CH₃; R₉′, R₁₀′, R₁₂′, R₁₃′, and R₁₄′=H; (16) R₁₁′, R₁₂′, andR₁₅′=CH₃; R₉′, R₁₀′, R₁₃′, R₁₄′, and R₁₆′=H (wherein the primed Rvariables represent the second occurrence of these —H or —CH₃ groups,since the moieties occur on each side of the oxygen atom); and the like.

Also suitable as second isocyanate-derived compounds are materialsdisclosed in U.S. Pat. No. 6,534,128, the disclosure of which is totallyincorporated herein by reference.

The second isocyanate-derived compound is present in the phase changeink carrier in any desired or effective amount, in one embodiment atleast about 0.5 percent by weight of the carrier, in another embodimentat least about 0.75 percent by weight of the carrier, and in yet anotherembodiment at least about 1 percent by weight of the carrier, and in oneembodiment no more than about 20 percent by weight of the carrier, inanother embodiment no more than about 15 percent by weight of thecarrier, and in yet another embodiment no more than about 10 percent byweight of the carrier, although the amount can be outside of theseranges.

In one specific embodiment, the phase change carrier composition canalso, if desired, contain an optional phase change inducing component.This component is referred to as a phase change inducing componentbecause it influences the phase change transition temperature. The phasechange inducing component is miscible with the other ink components andis a solid at the drum temperature at the time when the ink is jettedonto the drum in embodiments when the ink is used in printing processeswherein the substrate is an intermediate transfer member, and is a solidat the temperature of the final recording sheet in embodiments when thesubstrate is a final recording sheet. The phase change inducingcomponent is a molecule with at least one hydroxyl group and has aminimum melting point of about 40° C. Examples of suitable phase changeinducing components include (but are not limited to) alcohols of theformula R_(c)—OH wherein R_(c) is (i) an alkyl group (including linearand branched, cyclic and acyclic, and substituted and unsubstitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least about 1carbon atom, in another embodiment with at least about 5 carbon atoms,in yet another embodiment with at least about 10 carbon atoms, and instill another embodiment with at least about 15 carbon atoms, and in oneembodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 80 carbon atoms, and in yet anotherembodiment with no more than about 60 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (ii) an aryl group(including substituted and unsubstituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the aryl group), in oneembodiment with at least about 5 carbon atoms, in another embodimentwith at least about 6 carbon atoms, and in yet another embodiment withat least about 10 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 25carbon atoms, and in yet another embodiment with no more than about 12carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (iii) an arylalkyl group (including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (iv) an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, whereinthe alkyl portion of the alkylaryl group can be linear or branched,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either the aryl or the alkylportion of the alkylaryl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, wherein thesubstituents on the substituted alkyl, arylalkyl, and alkylaryl groupscan be (but are not limited to) hydroxy groups, halogen atoms, iminegroups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, aldehyde groups, ketone groups, ester groups,amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups,sulfonate groups, sulfide groups, sulfoxide groups, phosphine groups,phosphonium groups, phosphate groups, nitrile groups, mercapto groups,nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, azo groups, cyanato groups, isocyanatogroups, thiocyanato groups, isothiocyanato groups, carboxylate groups,mixtures thereof, and the like, wherein two or more substituents can bejoined together to form a ring.

Specific examples of suitable phase change inducing alcohols include1,10-decanediol, commercially available from Sigma-Aldrich, Milwaukee,Wis., 1,12-dodecanediol, commercially available from Sigma-Aldrich,1,2-dodecanediol, commercially available from Sigma-Aldrich, UNILIN®350, 425, 550, and 700, which are mixtures of linear primary alcoholswith average molecular weights of about 350, 425, 550, and 700,respectively, commercially available from Baker Petrolite, Sand Springs,Okla., polycaprolactone diols, of the general formula

including those having M_(n) values of about 530, 1,250, and 2,000,commercially available from Sigma-Aldrich, polycaprolactone diols, ofthe general formula

including those having M_(n) values of about 300 and 900, commerciallyavailable from Sigma-Aldrich, heptadecanol (all isomers), octadecanol(all isomers), nonadecanol (all isomers), eicosanol (C₂₀H₄₁OH; allisomers), heneicosanol (C₂₁H₄₃OH; all isomers), docosanol (C₂₂H₄₅OH; allisomers), dimer diols believed to be of the formula HO—C₃₆H_(64+n)—OHwherein C₃₆H_(64+n) is a branched alkylene group which may includeunsaturations and cyclic groups, wherein n is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, or 10, including but not limited to isomers of theformulae

commercially available from Uniqema Chemicals, New Castle, Del., Guerbetalcohols, which are 2,2-dialkyl-1-ethanols, including (but not limitedto) those of the general formula

wherein m+n is greater than or equal to 10, in one embodiment being fromabout 16 to about 36, commercially available from Tomah Chemicals andJarchem Industries Inc., Newark, N.J., and the like, as well as mixturesthereof.

One specific example of a phase change inducing component ishydrogenated castor oil, a triol triester believed to be of the formula

When present, the optional phase change inducing component is present inthe phase change ink carrier in any desired or effective amounteffective to influence the phase change transition temperature, in oneembodiment at least about 5 percent by weight of the carrier, in anotherembodiment at least about 10 percent by weight of the carrier, in yetanother embodiment at least about 20 percent by weight of the carrier,and in still another embodiment at least about 30 percent by weight ofthe carrier, and in one embodiment no more than about 98 percent byweight of the carrier, in another embodiment no more than about 80percent by weight of the carrier, in yet another embodiment no more thanabout 60 percent by weight of the carrier, in still another embodimentno more than about 50 percent by weight of the carrier, and in anotherembodiment no more than about 40 percent by weight of the carrier,although the amount can be outside of these ranges.

In another specific embodiment, the phase change carrier composition canalso, if desired, contain an optional curable viscosity modifying ester.These materials can help to reduce the viscosity of the ink at jettingtemperatures and, because they are equipped with ethylenicunsaturations, also enhance the curability of the ink. In addition, manyesters are neutral molecules; accordingly, in embodiments not containingbasic functional groups, they do not disrupt acid catalyzed cationiccuring mechanisms, as would molecules containing basic functionalgroups, such as amides, urethanes, ureas, or the like. Examples ofsuitable curable viscosity modifying esters include (but are not limitedto) those of the formula

wherein R_(a) is (i) an alkyl group (including linear and branched,cyclic and acyclic, and substituted and unsubstituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylgroup), in one embodiment with at least 1 carbon atom, in anotherembodiment with at least about 10 carbon atoms, and in yet anotherembodiment with at least about 16 carbon atoms, and in one embodimentwith no more than about 100 carbon atoms, in another embodiment with nomore than about 75 carbon atoms, and in yet another embodiment with nomore than about 50 carbon atoms, although the number of carbon atoms canbe outside of these ranges, (ii) an arylalkyl group (includingsubstituted and unsubstituted arylalkyl groups, wherein the alkylportion of the arylalkyl group can be linear or branched, cyclic oracyclic, and substituted or unsubstituted, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkyl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (iii) an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, whereinthe alkyl portion of the alkylaryl group can be linear or branched,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either the aryl or the alkylportion of the alkylaryl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, and wherein R_(b)is (i) an alkyl group having at least one ethylenic unsaturation therein(including linear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at leastabout 5 carbon atoms, and in another embodiment with at least about 6carbon atoms, and in one embodiment with no more than about 100 carbonatoms, in another embodiment with no more than about 75 carbon atoms,and in yet another embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges, (ii)an arylalkyl group having at least one ethylenic unsaturation therein(including substituted and unsubstituted arylalkyl groups, wherein thealkyl portion of the arylalkyl group can be linear or branched, cyclicor acyclic, and substituted or unsubstituted, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkyl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (iii) an alkylarylgroup having at least one ethylenic unsaturation therein (includingsubstituted and unsubstituted alkylaryl groups, wherein the alkylportion of the alkylaryl group can be linear or branched, cyclic oracyclic, and substituted or unsubstituted, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either the aryl or the alkyl portionof the alkylaryl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, wherein the substituentson the substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be(but are not limited to) hydroxy groups, halogen atoms, imine groups,ammonium groups, cyano groups, pyridine groups, pyridinium groups, ethergroups, aldehyde groups, ketone groups, ester groups, amide groups,carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups,sulfonic acid groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, nitrile groups, mercaptogroups, nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, azo groups, cyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.

Specific examples of suitable curable viscosity modifying esters includebis[4-(vinyloxy)butyl] adipate, of the formula

commercially available as VEctomer® 4060 and VEctomer® 4230 from MorflexInc., Greensboro, N.C., 4-[(vinyloxy)butyl]stearate, of the formula

commercially available as VEctomer® 3080 from Morflex Inc.,tris[4-(vinyloxy)butyl]trimellitate, of the formula

commercially available as VEctomer® 5015 from Morflex Inc.,bis[4-(vinyloxy)butyl]dodecanedioate, of the formula

and the like, as well as mixtures thereof.

When present, the curable viscosity modifying ester is present in thephase change ink carrier in any desired or effective amount, in oneembodiment at least about 1 percent by weight of the carrier, in anotherembodiment at least about 5 percent by weight of the carrier, and in yetanother embodiment at least about 10 percent by weight of the carrier,and in one embodiment no more than about 30 percent by weight of thecarrier, in another embodiment no more than about 25 percent by weightof the carrier, and in yet another embodiment no more than about 20percent by weight of the carrier, although the amount can be outside ofthese ranges.

Examples of additional suitable ink carrier materials include fattyamides, such as monoamides, tetra-amides, mixtures thereof, and thelike. Specific examples of suitable fatty amide ink carrier materialsinclude stearyl stearamide, a dimer acid based tetra-amide that is thereaction product of dimer acid, ethylene diamine, and stearic acid, adimer acid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and a carboxylic acid having at least about 36 carbonatoms, and the like, as well as mixtures thereof. When the fatty amideink carrier is a dimer acid based tetra-amide that is the reactionproduct of dimer acid, ethylene diamine, and a carboxylic acid having atleast about 36 carbon atoms, the carboxylic acid is of the generalformula

wherein R is an alkyl group, including linear, branched, saturated,unsaturated, and cyclic alkyl groups, said alkyl group in one embodimenthaving at least about 36 carbon atoms, in another embodiment having atleast about 40 carbon atoms, said alkyl group in one embodiment havingno more than about 200 carbon atoms, in another embodiment having nomore than about 150 carbon atoms, and in yet another embodiment havingno more than about 100 carbon atoms, although the number of carbon atomscan be outside of these ranges. Carboxylic acids of this formula arecommercially available from, for example, Baker Petrolite, Tulsa, Okla.,and can also be prepared as described in Example 1 of U.S. Pat. No.6,174,937, the disclosure of which is totally incorporated herein byreference. Further information on fatty amide carrier materials isdisclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No.4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat.No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S.Pat. No. 6,174,937, and British Patent GB 2 238 792, the disclosures ofeach of which are totally incorporated herein by reference.

Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO 96/14364, PCT Publication WO 97/33943, andPCT Publication WO 95/04760, the disclosures of each of which aretotally incorporated herein by reference.

Additional suitable phase change ink carrier materials includeparaffins, microcrystalline waxes, polyethylene waxes, ester waxes,amide waxes, fatty acids, fatty alcohols, fatty amides and other waxymaterials, sulfonamide materials, resinous materials made from differentnatural sources (such as, for example, tall oil rosins and rosinesters), and many synthetic resins, oligomers, polymers and copolymers,such as ethylene/vinyl acetate copolymers, ethylene/acrylic acidcopolymers, ethylene/vinyl acetate/acrylic acid copolymers, copolymersof acrylic acid with polyamides, and the like, ionomers, and the like,as well as mixtures thereof. One or more of these materials can also beemployed in a mixture with a fatty amide material and/or anisocyanate-derived material.

The ink carrier can also optionally contain an antioxidant. The optionalantioxidants protect the images from oxidation and also protect the inkcomponents from oxidation during the heating portion of the inkpreparation process. Specific examples of suitable antioxidants includeNAUGUARD® 524, NAUGUARD® 76, and NAUGUARD® 512 (commercially availablefrom Uniroyal Chemical Company, Oxford, Conn.), IRGANOX® 1010(commercially available from Ciba Geigy), and the like. When present,the optional antioxidant is present in the ink in any desired oreffective amount, in one embodiment of at least about 0.01 percent byweight of the ink carrier, in another embodiment of at least about 0.1percent by weight of the ink carrier, and in yet another embodiment ofat least about 1 percent by weight of the ink carrier, and in oneembodiment of no more than about 20 percent by weight of the inkcarrier, in another embodiment of no more than about 5 percent by weightof the ink carrier, and in yet another embodiment of no more than about3 percent by weight of the ink carrier, although the amount can beoutside of these ranges.

The ink carrier can also optionally contain an auxiliary viscositymodifier. Examples of suitable auxiliary viscosity modifiers includealiphatic ketones, such as stearone, and the like. When present, theoptional auxiliary viscosity modifier is present in the ink in anydesired or effective amount, in one embodiment of at least about 0.1percent by weight of the ink carrier, in another embodiment of at leastabout 1 percent by weight of the ink carrier, and in yet anotherembodiment of at least about 10 percent by weight of the ink carrier,and in one embodiment of no more than about 99 percent by weight of theink carrier, in another embodiment of no more than about 30 percent byweight of the ink carrier, and in yet another embodiment of no more thanabout 15 percent by weight of the ink carrier, although the amount canbe outside of these ranges.

Other optional additives to the ink carrier include clarifiers, such asUNION CAMP® X37-523-235 (commercially available from Union Camp), in anamount in one embodiment of at least about 0.01 percent by weight of theink carrier, in another embodiment of at least about 0.1 percent byweight of the ink carrier, and in yet another embodiment of at leastabout 5 percent by weight of the ink carrier, and in one embodiment ofno more than about 98 percent by weight of the ink carrier, in anotherembodiment of no more than about 50 percent by weight of the inkcarrier, and in yet another embodiment of no more than about 10 percentby weight of the ink carrier, although the amount can be outside ofthese ranges, tackifiers, such as FORAL® 85, a glycerol ester ofhydrogenated abietic (rosin) acid (commercially available fromHercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin)acid (commercially available from Hercules), CELLOLYN® 21, ahydroabietic (rosin) alcohol ester of phthalic acid (commerciallyavailable from Hercules), ARAKAWA KE-311 and KE-100 Resins,triglycerides of hydrogenated abietic (rosin) acid (commerciallyavailable from Arakawa Chemical Industries, Ltd.), synthetic polyterpeneresins such as NEVTAC® 2300, NEVTAC® 100, and NEVTAC® 80 (commerciallyavailable from Neville Chemical Company), WINGTACK® 86, a modifiedsynthetic polyterpene resin (commercially available from Goodyear), andthe like, in an amount in one embodiment of at least about 0.1 percentby weight of the ink carrier, in another embodiment of at least about 5percent by weight of the ink carrier, and in yet another embodiment ofat least about 10 percent by weight of the ink carrier, and in oneembodiment of no more than about 98 percent by weight of the inkcarrier, in another embodiment of no more than about 75 percent byweight of the ink carrier, and in yet another embodiment of no more thanabout 50 percent by weight of the ink carrier, although the amount canbe outside of these range, adhesives, such as VERSAMID® 757, 759, or 744(commercially available from Henkel), in an amount in one embodiment ofat least about 0.1 percent by weight of the ink carrier, in anotherembodiment of at least about 1 percent by weight of the ink carrier, andin yet another embodiment of at least about 5 percent by weight of theink carrier, and in one embodiment of no more than about 98 percent byweight of the ink carrier, in another embodiment of no more than about50 percent by weight of the ink carrier, and in yet another embodimentof no more than about 10 percent by weight of the ink carrier, althoughthe amount can be outside of these ranges, plasticizers, such asUNIPLEX® 250 (commercially available from Uniplex), the phthalate esterplasticizers commercially available from Monsanto under the trade nameSANTICIZER®, such as dioctyl phthalate, diundecyl phthalate, alkylbenzylphthalate (SANTICIZER® 278), triphenyl phosphate (commercially availablefrom Monsanto), KP-140®, a tributoxyethyl phosphate (commerciallyavailable from FMC Corporation), MORFLEX® 150, a dicyclohexyl phthalate(commercially available from Morflex Chemical Company Inc.), trioctyltrimellitate (commercially available from Eastman Kodak Co.), and thelike, in an amount in one embodiment of at least about 0.1 percent byweight of the ink carrier, in another embodiment of at least about 1percent by weight of the ink carrier, and in yet another embodiment ofat least about 2 percent by weight of the ink carrier, and in oneembodiment of no more than about 50 percent by weight of the inkcarrier, in another embodiment of no more than about 30 percent byweight of the ink carrier, and in yet another embodiment of no more thanabout 10 percent by weight of the ink carrier, although the amount canbe outside of these ranges, and the like.

The ink compositions further contain an initiator.

Examples of free radical initiators include benzyl ketones, monomerichydroxyl ketones, polymeric hydroxyl ketones, α-amino ketones, acylphosphine oxides, metallocenes, benzophenone, benzophenone derivatives,and the like. Specific examples include1-hydroxy-cyclohexylphenylketone, benzophenone,2-benzyl-2-(dimethylamino)-1-(4-(4-morphorlinyl)phenyl)-1-butanone,2-methyl-1-(4-methylthio)phenyl-2-(4-morphorlinyl)-1-propanone,diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide, benzyl-dimethylketal,isopropylthioxanthone, and the like, as well as mixtures thereof.

Examples of cationic initiators include aryldiazonium salts,diaryliodonium salts, triaylsulfonium salts, triarylselenonium salts,dialkylphenacylsulfonium salts, triarylsulfoxonium salts,aryloxydiarylsulfonium salts, and the like. Specific examples includetriphenylsulfonium hexaflurophosphate, methyldiphenylsulfoniumhexafluorophosphate, dimethylphenylsulfonium hexaflurophosphate,diphenyinapththylsulfonium hexaflurophosphate,di(methoxynapththyl)methylsulfonium hexaflurophosphate,(4-octyloxyphenyl) phenyl iodonium hexafluoro antimonate,(4-octyloxyphenyl) diphenyl sulfonium hexafluoro antimonate,(4-decyloxyphenyl) phenyl iodonium hexafluoro antimonite,(4-dodecyloxyphenyl) diphenyl sulfonium hexafluoroantimonate, and thelike, as well as mixtures thereof.

The initiator is present in the phase change ink carrier in any desiredor effective amount, in one embodiment at least about 0.1 percent byweight of the carrier, in another embodiment at least about 1 percent byweight of the carrier, in yet another embodiment at least about 5percent by weight of the carrier, and in still another embodiment atleast about 10 percent by weight of the carrier, and in one embodimentno more than about 20 percent by weight of the carrier, in anotherembodiment no more than about 17 percent by weight of the carrier, andin yet another embodiment no more than about 15 percent by weight of thecarrier, although the amount can be outside of these ranges.

The ink carrier is present in the phase change ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 50 percent byweight of the ink, and in yet another embodiment of at least about 90percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 98 percent by weight of the ink, and in yet anotherembodiment of no more than about 95 percent by weight of the ink,although the amount can be outside of these ranges.

The phase change inks also contain a colorant. Any desired or effectivecolorant can be employed, including dyes, pigments, mixtures thereof,and the like, provided that the colorant can be dissolved or dispersedin the ink vehicle. The phase change carrier compositions can be used incombination with conventional phase change ink colorant materials, suchas Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acid andDirect Dyes, Basic Dyes, Sulphur Dyes, Vat Dyes, and the like. Examplesof suitable dyes include Neozapon Red 492 (BASF); Orasol Red G(Ciba-Geigy); Direct Brilliant Pink B (Crompton & Knowles); Aizen SpilonRed C-BH (Hodogaya Chemical); Kayanol Red 3BL (Nippon Kayaku); LevanolBrilliant Red 3BW (Mobay Chemical); Levaderm Lemon Yellow (MobayChemical); Spirit Fast Yellow 3G; Aizen Spilon Yellow C-GNH (HodogayaChemical); Sirius Supra Yellow GD 167; Cartasol Brilliant Yellow 4GF(Sandoz); Pergasol Yellow CGP (Ciba-Geigy); Orasol Black RLP(Ciba-Geigy); Savinyl Black RLS (Sandoz); Dermacarbon 2GT (Sandoz);Pyrazol Black BG (ICI); Morfast Black Conc. A (Morton-Thiokol); DiaazolBlack RN Quad (ICI); Orasol Blue GN (Ciba-Geigy); Savinyl Blue GLS(Sandoz); Luxol Blue MBSN (Morton-Thiokol); Sevron Blue 5GMF (ICI);Basacid Blue 750 (BASF), Neozapon Black X51 [C.I. Solvent Black, C.I.12195] (BASF), Sudan Blue 670 [C.I. 61554] (BASF), Sudan Yellow 146[C.I. 12700] (BASF), Sudan Red 462 [C.I. 26050] (BASF), IntrathermYellow 346 from Crompton and Knowles, C.I. Disperse Yellow 238, NeptuneRed Base NB543 (BASF, C.I. Solvent Red 49), Neopen Blue FF-4012 fromBASF, Neopen Blue 808 (BASF), Spectra Oil Blue ZV dyes, Lampronol BlackBR from ICI (C.I. Solvent Black 35), Morton Morplas Magenta 36 (C.I.Solvent Red 172), metal phthalocyanine colorants such as those disclosedin U.S. Pat. No. 6,221,137, the disclosure of which is totallyincorporated herein by reference, and the like. Polymeric dyes can alsobe used, such as those disclosed in, for example, U.S. Pat. No.5,621,022 and U.S. Pat. No. 5,231,135, the disclosures of each of whichare totally incorporated herein by reference, and commercially availablefrom, for example, Milliken & Company as Milliken Ink Yellow 12,Milliken Ink Blue 92, Milliken Ink Red 357, Milliken Ink Yellow 1800,Milliken Ink Black 8915-67, uncut Reactant Orange X-38, uncut ReactantBlue X-17, Solvent Yellow 162, Acid Red 52, Solvent Blue 44, and uncutReactant Violet X-80.

Pigments are also suitable colorants for the phase change inks. Examplesof suitable pigments include Violet Toner VT-8015 (Paul Uhlich);Paliogen Violet 5100 (BASF); Paliogen Violet 5890 (BASF); PermanentViolet VT 2645 (Paul Uhlich); Heliogen Green L8730 (BASF); Argyle GreenXP-111-S (Paul Uhlich); Brilliant Green Toner GR 0991 (Paul Uhlich);Lithol Scarlet D3700 (BASF); Toluidine Red (Sigma-Aldrich); Scarlet forThermoplast NSD PS PA (Ugine Kuhlmann of Canada); E.D. Toluidine Red(Sigma-Aldrich); Lithol Rubine Toner (Paul Uhlich); Lithol Scarlet 4440(BASF); Bon Red C (Dominion Color Company); Royal Brilliant Red RD-8192(Paul Uhlich); Oracet Pink RF (Ciba-Geigy); Paliogen Red 3871K (BASF);Paliogen Red 3340 (BASF); Lithol Fast Scarlet L4300 (BASF); HeliogenBlue L6900, L7020 (BASF); Heliogen Blue K6902, K6910 (BASF); HeliogenBlue D6840, D7080 (BASF); Sudan Blue OS (BASF); Neopen Blue FF4012(BASF); PV Fast Blue B2G01 (American Hoechst); Irgalite Blue BCA(Ciba-Geigy); Paliogen Blue 6470 (BASF); Sudan III (Red Orange)(Matheson, Colemen Bell); Sudan II (Orange) (Matheson, Colemen Bell);Sudan Orange G (Sigma-Aldrich), Sudan Orange 220 (BASF); Paliogen Orange3040 (BASF); Ortho Orange OR 2673 (Paul Uhlich); Paliogen Yellow 152,1560 (BASF); Lithol Fast Yellow 0991K (BASF); Paliotol Yellow 1840(BASF); Novoperm Yellow FGL (Hoechst); Permanent Yellow YE 0305 (PaulUhlich); Lumogen Yellow D0790 (BASF); Suco-Yellow L1250 (BASF);Suco-Yellow D1355 (BASF); Suco Fast Yellow D1355, D1351 (BASF);Hostaperm Pink E (American Hoechst); Fanal Pink D4830 (BASF); CinquasiaMagenta (Du Pont); Paliogen Black L0084 (BASF); Pigment Black K801(BASF); and carbon blacks such as REGAL 330® (Cabot), Carbon Black 5250,Carbon Black 5750 (Columbia Chemical), and the like.

Also suitable are the colorants disclosed in U.S. Pat. No. 6,472,523,U.S. Pat. No. 6,726,755, U.S. Pat. No. 6,476,219, U.S. Pat. No.6,576,747, U.S. Pat. No. 6,713,614, U.S. Pat. No. 6,663,703, U.S. Pat.No. 6,755,902, U.S. Pat. No. 6,590,082, U.S. Pat. No. 6,696,552, U.S.Pat. No. 6,576,748, U.S. Pat. No. 6,646,111, U.S. Pat. No. 6,673,139,Copending Application U.S. Ser. No. 10/260,146, filed Sep. 27, 2002,entitled “Colorant Compounds,” and Copending Application U.S. Ser. No.10/260,379, filed Sep. 27, 2002, entitled “Methods for Making ColorantCompounds,” the disclosures of each of which are totally incorporatedherein by reference.

Other ink colors besides the subtractive primary colors can be desirablefor applications such as postal marking, industrial marking, andlabelling using phase change printing, and the inks are applicable tothese needs. Further, infrared (IR) or ultraviolet (UV) absorbing dyescan also be incorporated into the inks for use in applications such as“invisible” coding or marking of products. Examples of such infrared andultraviolet absorbing dyes are disclosed in, for example, U.S. Pat. No.5,378,574, U.S. Pat. No. 5,146,087, U.S. Pat. No. 5,145,518, U.S. Pat.No. 5,543,177, U.S. Pat. No. 5,225,900, U.S. Pat. No. 5,301,044, U.S.Pat. No. 5,286,286, U.S. Pat. No. 5,275,647, U.S. Pat. No. 5,208,630,U.S. Pat. No. 5,202,265, U.S. Pat. No. 5,271,764, U.S. Pat. No.5,256,193, U.S. Pat. No. 5,385,803, and U.S. Pat. No. 5,554,480, thedisclosures of each of which are totally incorporated herein byreference.

In a specific embodiment, the colorant is an isocyanate-derived coloredresin as disclosed in, for example, U.S. Pat. No. 5,780,528 and U.S.Pat. No. 5,919,839, the disclosures of each of which are totallyincorporated herein by reference. In this embodiment, the colorant isthe reaction product of a hydroxyl-substituted or primary or secondaryamino-substituted chromophore with an isocyanate. Examples of suitableisocyanates include monoisocyanates, diisocyanates, triisocyanates,copolymers of a diisocyanate, copolymers of a triisocyanate,polyisocyanates (having more than three isocyanate functional groups),and the like, as well as mixtures thereof. Specific examples of suitableisocyanates include those listed hereinabove as being suitable forreaction with the hydroxyl-substituted or amino-substituted antioxidant.Examples of suitable hydroxyl-substituted and primary or secondaryamino-substituted chromophores include those disclosed in, for example,U.S. Pat. No. 3,157,633, U.S. Pat. No. 3,927,044, U.S. Pat. No.3,994,835, U.S. Pat. No. 4,102,644, U.S. Pat. No. 4,113,721, U.S. Pat.No. 4,132,840, U.S. Pat. No. 4,137,243, U.S. Pat. No. 4,170,564, U.S.Pat. No. 4,284,729, U.S. Pat. No. 4,507,407, U.S. Pat. No. 4,640,690,U.S. Pat. No. 4,732,570, U.S. Pat. No. 4,751,254, U.S. Pat. No.4,751,254, U.S. Pat. No. 4,761,502, U.S. Pat. No. 4,775,748, U.S. Pat.No. 4,812,141, U.S. Pat. No. 4,846,846, U.S. Pat. No. 4,871,371, U.S.Pat. No. 4,912,203, U.S. Pat. No. 4,978,362, U.S. Pat. No. 5,043,013,U.S. Pat. No. 5,059,244, U.S. Pat. No. 5,149,800, U.S. Pat. No.5,177,200, U.S. Pat. No. 5,270,363, U.S. Pat. No. 5,290,921, and U.S.Pat. No. 5,731,398, the disclosures of each of which are totallyincorporated herein by reference. Hydroxyl-containing and primary orsecondary amino-containing colorants from the classes of Color Index(C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, BasicDyes, Sulphur Dyes, Vat Dyes, and the like can also be used.

In another specific embodiment, the colorant is a curable olefincolorant such as those disclosed in U.S. Pat. No. 6,870,063, U.S. Pat.No. 6,870,062, U.S. Pat. No. 6,787,658, and U.S. Patent Publication20040142995, the disclosures of each of which are totally incorporatedherein by reference.

The colorant is present in the phase change ink in any desired oreffective amount to obtain the desired color or hue, in one embodimentat least about 0.1 percent by weight of the ink, in another embodimentat least about 0.2 percent by weight of the ink, and in anotherembodiment at least about 0.5 percent by weight of the ink, and in oneembodiment no more than about 50 percent by weight of the ink, inanother embodiment no more than about 20 percent by weight of the ink,in yet another embodiment no more than about 10 percent by weight of theink, and in still another embodiment no more than about 5 percent byweight of the ink, although the amount can be outside of these ranges.

Curing of the ink can be effected by exposure of the ink image toactinic radiation at any desired or effective wavelength, in oneembodiment at least about 200 nanometers, and one embodiment no morethan about 480 nanometers, although the wavelength can be outside ofthese ranges. Exposure to actinic radiation can be for any desired oreffective period of time, in one embodiment for at least about 1 second,and in another embodiment for at least about 5 seconds, and in oneembodiment for no more than about 30 seconds, and in another embodimentfor no more than about 15 seconds, although the exposure period can beoutside of these ranges. By curing is meant that the isocyanate-basedcurable compound undergoes an increase in molecular weight upon exposureto actinic radiation, such as (but not limited to) crosslinking, chainlengthening, or the like.

The ink compositions in one embodiment have melting points of no lowerthan about 50° C., in another embodiment of no lower than about 70° C.,and in yet another embodiment of no lower than about 80° C., and havemelting points in one embodiment of no higher than about 120° C., inanother embodiment of no higher than about 110° C., and in yet anotherembodiment of no higher than about 100° C., although the melting pointcan be outside of these ranges.

The ink compositions generally have melt viscosities at the jettingtemperature (in one embodiment no lower than about 50° C., in anotherembodiment no lower than about 60° C., and in yet another embodiment nolower than about 70° C., and in one embodiment no higher than about 120°C., and in another embodiment no higher than about 110° C., although thejetting temperature can be outside of these ranges) in one embodiment ofno more than about 30 centipoise, in another embodiment of no more thanabout 20 centipoise, and in yet another embodiment of no more than about15 centipoise, and in one embodiment of no less than about 2 centipoise,in another embodiment of no less than about 5 centipoise, and in yetanother embodiment of no less than about 7 centipoise, although the meltviscosity can be outside of these ranges.

For printing applications wherein the ink is printed onto anintermediate transfer member and subsequently transferred to a finalsubstrate, the viscosity of the ink in one specific embodiment increasesto about 10⁶ centipoise or greater at the intermediate transfer membertemperature to facilitate adhesion to the intermediate transfer member,and for printing applications wherein the ink is printed directly onto afinal substrate, the viscosity of the ink in one specific embodimentincreases to 10⁶ centipoise or greater at the final substratetemperature to prevent the ink from soaking into the final substrateand/or to facilitate adhesion to the final substrate until curing byexposure to radiation. In one specific embodiment, the temperature ofthe intermediate transfer member or the final substrate onto which theink is printed and at which the ink viscosity increases to about 10⁶centipoise or greater is about 50° C. or lower.

The ink compositions can be prepared by any desired or suitable method.For example, the ink ingredients can be mixed together, followed byheating, to a temperature in one embodiment of at least about 80° C.,and in one embodiment of no more than about 120° C., although thetemperature can be outside of these ranges, and stirring until ahomogeneous ink composition is obtained, followed by cooling the ink toambient temperature (typically from about 20 to about 25° C.). The inksare solid at ambient temperature. In a specific embodiment, during theformation process, the inks in their molten state are poured into moldsand then allowed to cool and solidify to form ink sticks.

The inks can be employed in apparatus for direct printing ink jetprocesses and in indirect (offset) printing ink jet applications.Another embodiment disclosed herein is directed to a process whichcomprises incorporating an ink as disclosed herein into an ink jetprinting apparatus, melting the ink, and causing droplets of the meltedink to be ejected in an imagewise pattern onto a recording substrate. Adirect printing process is also disclosed in, for example, U.S. Pat. No.5,195,430, the disclosure of which is totally incorporated herein byreference. Yet another embodiment disclosed herein is directed to aprocess which comprises incorporating an ink as disclosed herein into anink jet printing apparatus, melting the ink, causing droplets of themelted ink to be ejected in an imagewise pattern onto an intermediatetransfer member, and transferring the ink in the imagewise pattern fromthe intermediate transfer member to a final recording substrate. In aspecific embodiment, the intermediate transfer member is heated to atemperature above that of the final recording sheet and below that ofthe melted ink in the printing apparatus. An offset or indirect printingprocess is also disclosed in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference. In onespecific embodiment, the printing apparatus employs a piezoelectricprinting process wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.Inks as disclosed herein can also be employed in other hot melt printingprocesses, such as hot melt acoustic ink jet printing, hot melt thermalink jet printing, hot melt continuous stream or deflection ink jetprinting, and the like. Phase change inks as disclosed herein can alsobe used in printing processes other than hot melt ink jet printingprocesses.

Any suitable substrate or recording sheet can be employed, includingplain papers such as XEROX® 4024 papers, XEROX® Image Series papers,Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coatedpapers such as Sharp Company silica coated paper, JuJo paper, HAMMERMILLLASERPRINT® paper, and the like, transparency materials, fabrics,textile products, plastics, polymeric films, inorganic substrates suchas metals and wood, and the like.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and the claims are not limited to thematerials, conditions, or process parameters set forth in theseembodiments. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I

50.0 g (0.225 mol) of isophorone diisocyanate (Desmodur I, obtained fromBayer Corp., Pittsburgh, Pa.) and 49.6 g (0.428 mol) of 1,4 butanediolvinyl ether (obtained from Sigma-Aldrich Chemical Company, Milwaukee,Wis.) were charged to a 200 ml beaker equipped with magnetic stir bar.The beaker was placed in a 110° C. silicone oil bath on a stirring hotplate and stirring was initiated. Five drops of catalyst (Fascat 4202dibutyltindilaurate, obtained from Elf Atochem North America, Inc.,Philadelphia, Pa.) were added and the mixture was allowed to react forabout 2 h at 110° C. An FT-IR analysis of the reaction product indicatedthat almost all of the NCO functionality was consumed. 9.1 g (0.034 mol)of octadecyl alcohol (obtained from Sigma-Aldrich Chemical Co.) wasadded and the mixture was allowed to react for 1 additional hour. AnFT-IR analysis of the reaction product indicated that all the NCOfunctionality was consumed. Specifically, the FT-IR showed the absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740-1680 cm⁻¹ and about1540-1530 cm⁻¹ corresponding to urethane frequencies. The final urethaneproduct was then poured into an aluminum pan and allowed to cool. Thisfinal product was characterized by a viscosity of about 16.15 cPs asmeasured by a Ferranti-Shirley cone-plate viscometer at about 135° C.The product was believed to be of the formula

EXAMPLE II

50.0 g (0.225 mol) of isophorone diisocyanate (Desmodur I, obtained fromBayer Corp., Pittsburgh, Pa.), 81.3 g (0.225 mol) of Abitol E(hydroabietyl alcohol, obtained from Hercules Inc., Wilmington, Del.),and 26.1 g (0.225 mol) of 1,4 butanediol vinyl ether (obtained fromSigma-Aldrich Chemical Company, Milwaukee, Wis.) were charged to a 400ml beaker equipped with magnetic stir bar. The beaker was placed in a110° C. silicone oil bath on a stirring hot plate and stirring wasinitiated. Five drops of catalyst (Fascat 4202 dibutyltindilaurate,obtained from Elf Atochem North America, Inc., Philadelphia, Pa.) wereadded and the mixture was allowed to react for about 2 hours at 110° C.An FT-IR analysis of the reaction product indicated that all the NCOfunctionality was consumed. Specifically, the FT-IR showed the absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740-1680 cm⁻¹ and about1540-1530 cm⁻¹ corresponding to urethane frequencies. The final urethaneproduct was then poured into an aluminum pan and allowed to cool. Thisfinal product was characterized by a viscosity of about 97.16 cPs asmeasured by a Ferranti-Shirley cone-plate viscometer at about 135° C.The product was believed to be of the formula

EXAMPLE III

62.3 g (0.371 mol) of hexamethylene diisocyanate (obtained fromSigma-Aldrich Chemical Co., Milwaukee, Wis.), 100.0 g (0.186 mol) ofdimer diol (PRIPOL 2033, obtained from Uniqema, New Castle Del.), and43.0 g (0.371 mol) of 1,4 butanediol vinyl ether (obtained fromSigma-Aldrich Chemical Company) were charged to a 400 ml beaker equippedwith magnetic stir bar. The beaker was placed in a 110° C. silicone oilbath on a stirring hot plate and stirring was initiated. Three drops ofcatalyst (Fascat 4202 dibutyltindilaurate, obtained from Elf AtochemNorth America, Inc., Philadelphia, Pa.) were added and the mixture wasallowed to react for about 2 hours at 110° C. An FT-IR analysis of thereaction product indicated that all the NCO functionality was consumed.Specifically, the FT-IR showed the absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding tourethane frequencies. The final urethane product was then poured into analuminum pan and allowed to cool. The product was believed to be of theformula

EXAMPLE IV

50.0 g (0.167 mol) of octadecyl isocyanate (Mondur O, obtained fromBayer Corp., Pittsburgh, Pa.) and 19.6 g (0.169 mol) of 1,4 butanediolvinyl ether (obtained from Sigma-Aldrich Chemical Co., Milwaukee, Wis.)were charged to a 200 ml beaker equipped with magnetic stir bar. Thebeaker was placed in a 110° C. silicone oil bath on a stirring hot plateand stirring was initiated. Two drops of catalyst (Fascat 4202dibutyltindilaurate, obtained from Elf Atochem North America, Inc.,Philadelphia, Pa.) were added and the mixture was allowed to react forabout 2 hours at 110° C. An FT-IR analysis of the reaction productindicated that all the NCO functionality was consumed. Specifically, theFT-IR showed the absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies. The final urethane product was then poured into an aluminumpan and allowed to cool. This final product was characterized by aviscosity of about 2.63 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 135° C. The product was believed to be of theformula

EXAMPLE V

50.0 g (0.167 mol) of octadecyl isocyanate (Mondur O, obtained fromBayer Corp., Pittsburgh, Pa.) and 31.0 g (0.168 mol) of undecylenic acid(obtained from Sigma-Aldrich Chemical Co., Milwaukee, Wis.) were chargedto a 200 ml beaker equipped with magnetic stir bar. The beaker wasplaced in a 110° C. silicone oil bath on a stirring hot plate andstirring was initiated. Two drops of catalyst (Fascat 4202dibutyltindilaurate, obtained from Elf Atochem North America, Inc.,Philadelphia, Pa.) were added and the mixture was allowed to react forabout 2 hours at 110° C. An FT-IR analysis of the reaction productindicated that all the NCO functionality was consumed. Specifically, theFT-IR showed the absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethane/amidefrequencies. The final amide product was then poured into an aluminumpan and allowed to cool. This final product was characterized by aviscosity of about 5.44 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 135° C. The product was believed to be of theformula

EXAMPLE VI

50.0 g (0.225 mol) of isophorone diisocyanate (Desmodur I, obtained fromBayer Corp., Pittsburgh, Pa.) and 46.0 g (0.431 mol) of 2-allyloxyethanol (obtained from Sigma-Aldrich Chemical Co., Milwaukee, Wis.) werecharged to a 200 ml beaker equipped with magnetic stir bar. The beakerwas placed in a 110° C. silicone oil bath on a stirring hot plate andstirring was initiated. One drop of catalyst (Fascat 4202dibutyltindilaurate, obtained from Elf Atochem North America, Inc.,Philadelphia, Pa.) was added and the mixture was allowed to react forabout 2 hours at 110° C. An FT-IR analysis of the reaction productindicated that all the NCO functionality was consumed. Specifically, theFT-IR showed the absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies. The final urethane product was then poured into an aluminumpan and allowed to cool. This final product was characterized by aviscosity of about 13.15 cPs as measured by a Ferranti-Shirleycone-plate viscometer at about 135° C. The product was believed to be ofthe formula

EXAMPLE VII

50.0 g (0.225 mol) of isophorone diisocyanate (Desmodur I, obtained fromBayer Corp., Pittsburgh, Pa.), 81.4 g (0.225 mol) of Abitol E(hydroabietyl alcohol, obtained from Hercules Inc., Wilmington, Del.),and 23.0 g (0.225 mol) of 2-allyloxy ethanol (obtained fromSigma-Aldrich Chemical Co., Milwaukee, Wis.) were charged to a 400 mlbeaker equipped with magnetic stir bar. The beaker was placed in a 110°C. silicone oil bath on a stirring hot plate and stirring was initiated.Five drops of catalyst (Fascat 4202 dibutyltindilaurate, obtained fromElf Atochem North America, Inc., Philadelphia, Pa.) were added and themixture was allowed to react for about 2 hours at 110° C. An FT-IRanalysis of the reaction product indicated that all the NCOfunctionality was consumed. Specifically, the FT-IR showed the absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740-1680 cm⁻¹ and about1540-1530 cm⁻¹ corresponding to urethane frequencies. The final urethaneproduct was then poured into an aluminum pan and allowed to cool. Thisfinal product was characterized by a viscosity of about 38.81 cPs asmeasured by a Ferranti-Shirley cone-plate viscometer at about 135° C.The product was believed to be of the formula

EXAMPLE VIII

52.8 g (0.178 mol) of octadecyl isocyanate (Mondur O, obtained fromBayer Corp., Pittsburgh, Pa.) and 18.2 g (0.178 mol) of allyloxy ethanol(obtained from Sigma-Aldrich Chemical Co., Milwaukee, Wis.) were chargedto a 200 ml beaker equipped with magnetic stir bar. The beaker wasplaced in a 110° C. silicone oil bath on a stirring hot plate andstirring was initiated. One drop of catalyst (Fascat 4202dibutyltindilaurate, obtained from Elf Atochem North America, Inc.,Philadelphia, Pa.) was added and the mixture was allowed to react forabout 2 hours at 110° C. An FT-IR analysis of the reaction productindicated that all the NCO functionality was consumed. Specifically, theFT-IR showed the absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies. The final urethane product was then poured into an aluminumpan and allowed to cool. This final product was characterized by aviscosity of about 2.63 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 135° C. The product was believed to be of theformula

EXAMPLE IX

50.0 g (0.238 mol) of trimethyl-1,6-diisocyanatohexane (obtained fromSigma-Aldrich Chemical Co., Milwaukee, Wis.) and 55.2 g (0.476 mol) of1,4-butanediol vinyl ether (obtained from Sigma-Aldrich Chemical Co.)were charged to a 200 ml beaker equipped with magnetic stir bar. Thebeaker was placed in a 110° C. silicone oil bath on a stirring hot plateand stirring was initiated. Five drops of catalyst (Fascat 4202dibutyltindilaurate, obtained from Elf Atochem North America, Inc.,Philadelphia, Pa.) were added and the mixture was allowed to react forabout 2 hours at 110° C. An FT-IR analysis of the reaction productindicated that all the NCO functionality was consumed. Specifically, theFT-IR showed the absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies. The final urethane product was then poured into an aluminumpan and allowed to cool. The product was believed to be of the formulae

EXAMPLE X

50.0 g (0.298 mol) of hexamethylene diisocyanate (obtained fromSigma-Aldrich Chemical Co., Milwaukee, Wis.) and 69.0 g (0.595 mol) of1,4-butanediol vinyl ether (obtained from Sigma-Aldrich Chemical Co.)were charged to a 200 ml beaker equipped with magnetic stir bar. Thebeaker was placed in a 110° C. silicone oil bath on a stirring hot plateand stirring was initiated. Five drops of catalyst (Fascat 4202dibutyltindilaurate, obtained from Elf Atochem North America, Inc.,Philadelphia, Pa.) were added and the mixture was allowed to react forabout 2 hours at 110° C. An FT-IR analysis of the reaction productindicated that all the NCO functionality was consumed. Specifically, theFT-IR showed the absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies. The final urethane product was then poured into an aluminumpan and allowed to cool. The product was believed to be of the formula

EXAMPLE XI

The process of Example V is repeated except that the undecylenic acid isreplaced with 28.6 g (0.168 mol) of 9-decenoic acid (available fromSigma-Aldrich Chemical Co., Milwaukee, Wis.). It is believed that theproduct will be of the formula

EXAMPLE XII

About 117.7 g (1.351 moles) of monoethanolamine vinyl ether (availablefrom Alash Ltd., Temirtau, Kazakhstan) is added to a 1 L four-neck resinkettle equipped with a Trubore stirrer, an N₂ atmosphere inlet, additionfunnel (200 mL), and thermocouple-temperature controller. The kettle isthen heated to about 70° C. with stirring under an N₂ atmosphere and 150g (0.676 moles) of isophorone diisocyanate (Desmodur I, available fromBayer Corp., Pittsburgh, Pa.) is added to the addition funnel.Isophorone diisocyanate is then added dropwise to the monoethanolaminevinyl ether over 2 hours and the temperature is gradually increased toabout 165° C. as the viscosity increases. The contents are held at about165° C. for 1 hour and an FT-IR of the product is run to ensure that allof the NCO functionality is consumed. The absence (disappearance) of apeak at about 2285 cm⁻¹ (NCO) and the appearance (or increase inmagnitude) of peaks at about 1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹corresponding to urea frequencies are used to confirm completion of thereaction. The final di-urea resin product is poured into aluminum moldsand allowed to cool and harden. It is believed that the product will beof the formula

EXAMPLE XIII

The process of Example XII is repeated, adjusting the amount ofmonoethanolamine vinyl ether to about 58.9 g (0.676 mol) and replacingisophorone diisocyanate with about 199.8 g (0.676 mol) of octadecylisocyanate (available from Sigma-Aldrich Chemical Company, Milwaukee,Wis.). It is believed that the product will be of the formula

EXAMPLE XIV

39.3 g (0.338 moles) of 1,4-butanediol vinyl ether (available fromSigma-Aldrich Chemical Co., Milwaukee, Wis.) and about 75.1 g (0.338moles) of isophorone diisocyanate (Desmodur I, available from BayerCorp, Pittsburgh, Pa.) is added to a 500 mL three-neck resin kettleequipped with a Trubore stirrer, an N₂ atmosphere inlet, and athermocouple-temperature controller. Thereafter, agitation is begun,0.22 grams of catalyst (Fascat 4202; dibutyltindilaurate, available fromElf Atochem North America, Inc., Philadelphia, Pa.) is added, and thereaction mixture is heated to 90° C. under an N₂ atmosphere. After 1hour at 90° C., the temperature is increased to 110° C. and held for 2hours. 91.1 grams (0.338 moles) of octadecylamine (available fromSigma-Aldrich Chemical Co.) is then added and the temperature is raisedto 130° C. and held there for 2 hours. An FT-IR of the reaction productis thereafter run to ensure that all of the NCO functionality isconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹ corresponding to ureafrequencies and about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹corresponding to urethane frequencies are used to confirm completion ofthe reaction. The final mixed urethane/urea resin product is poured intoaluminum molds and allowed to cool and harden. It is believed that theproduct will be of the formula

EXAMPLE XV

The process of Example XIV is repeated except that the 1,4-butanediolvinyl ether is replaced with about 34.5 g (0.338 moles) of 2-allyloxyethanol (available from Sigma-Aldrich Chemical Co., Milwaukee, Wis.). Itis believed that the product will be of the formula

EXAMPLE XVI Synthesis of Bis[4-(vinyloxy)butyl]dodecanedioate

To a 1 liter, two neck flask equipped with a stir bar, argon inlet, andstopper was added dodecanedioic acid (10.0 grams, 43 mmol, obtained fromSigma-Aldrich, Milwaukee, Wis.), 1,4-butanediol vinyl ether (10.1 grams,87 mmol, obtained from Sigma-Aldrich), 4-(dimethylamino)pyridine (1.07gram, 8.8 mmol, obtained from Sigma-Aldrich), 1-hydroxybenzotriazole(1.18 gram, 8.7 mmol, obtained from Sigma-Aldrich) and methylenechloride (500 milliliters). The reaction mixture was cooled to 0° C. and1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (16.6grams, 87 mmol, obtained from Sigma-Aldrich) was added portionwise. Thereaction mixture was stirred at 0° C. for 0.5 hour, followed by stirringat room temperature until the reaction was deemed complete by ¹H NMRspectroscopy in DMSO-d₆ (about 2 hours); the signal corresponding to themethylene protons alpha to the carbonyl groups of 1,12-dodecanedioc acid(4H, triplet at δ2.18) was consumed and was replaced by a triplet atδ2.27 (4H), corresponding to [H₂C═CHO(CH₂)₄OOCCH ₂(CH₂)₄]₂. The reactionmixture was then concentrated in vacuo and the residue was dissolved inethyl acetate (300 milliliters). The organic layer was washed withsaturated sodium bicarbonate (2×150 milliliters) and water (2×150milliliters), dried over anhydrous sodium sulfate, filtered, andconcentrated in vacuo. The crude product was recrystallized frommethanol to afford 13.5 grams (73 percent yield) of a white solid(mp=42-43° C.). The product was believed to be of the formula

¹H NMR (300 MHz, CDCl₃): δ6.47 (2H, dd, J=14.3, 6.8 Hz), 4.19 (2H, dd,J=14.3, 1.9 Hz), 4.10 (4H, br. t, J=6.0 Hz), 4.00 (2H, dd, J=6.8, 1.9Hz), 3.70 (4H, br. t, J=5.7 Hz), 2.29 (4H, t, J=7.5 Hz), 1.76-1.71 (8H,m), 1.63-1.56 (4H, m), 1.28 (12H, br. s).

EXAMPLE XVII Synthesis ofBis[4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamate (Mixture of2,2,4- and 2,4,4-isomers)

To a 2 liter three neck flask equipped with a stopper, dropping funnel,stir bar, and reflux condenser was addedtrimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers,118.7 grams, 0.57 mol, obtained from Sigma-Aldrich, Milwaukee, Wis.),dibutyltin dilaurate (3.56 grams, 5.6 mmol, obtained from Sigma-Aldrich)and anhydrous tetrahydrofuran (1 liter). 1,4-Butanediol vinyl ether(133.2 grams, 1.2 mol, obtained from Sigma-Aldrich) was added slowlydropwise to the stirring solution via the addition funnel. The reactionmixture was brought to reflux and was kept at this temperature untildeemed complete by infrared spectroscopy (about 5 hours, confirmed bythe disappearance of the isocyanate peak at 2200 cm⁻¹). When thereaction was complete, methanol (500 milliliters) was added to quenchany residual isocyanate and the solution was stirred for 0.5 hour. Thesolvent was stripped in vacuo and the residual oil was triturated withhexane (3×500 milliliters), dissolved in methylene chloride (1 liter),washed with water (1×750 milliliters), dried over anhydrous magnesiumsulfate, filtered, and concentrated in vacuo to afford 221 grams of apale yellow oil (89 percent yield). The product was believed to be amixture of compounds of the formulae

¹ H NMR (300 MHz, CDCl₃): δ6.47 (2H, dd, J=14.3, 6.8 Hz), 4.88-4.62 (2H,br. m), 4.19 (2H, dd, J=14.3, 1.8 Hz), 4.09 (4H, br. s), 4.00 (2H, dd,J=6.8, 1.8 Hz), 3.70 (4H, br. s), 3.18-2.91 (4H, m), 1.72-1.01 (13H, m),1.01-0.88 (9H, m).

EXAMPLE XVIII

A compound of the formula

was prepared as follows. To a 1 L three neck flask equipped with a stirbar, dropping funnel reflux condenser, stopper, and argon inlet wasadded 1,6-diisocyanatohexane (26.84 g, 0.16 mol, obtained fromSigma-Aldrich, Milwaukee, Wis.) and anhydrous tetrahydrofuran (300 mL).To the stirring solution was added 1,4-butanediol vinyl ether (17.65 g,0.15 mol, obtained from Sigma-Aldrich) in anhydrous tetrahydrofuran (150mL) via the dropping funnel. When the addition was complete, dibutyltindilaurate (0.96 g, 1.5 mmol, obtained from Sigma-Aldrich) was added. Thereaction mixture was heated to 50° C. When 50% of the isocyanate groupswere consumed (peaks at aboutδ3.30 and δ3.16 in an approximately 1:1ratio on the ¹H NMR spectrum; reaction time approximately 15 minutes),the reaction mixture was cooled to room temperature andtrimethylolpropane (8.16 g, 61 mmol, obtained from Sigma-Aldrich) inanhydrous tetrahydrofuran (50 mL) was added slowly, dropwise to thereaction mixture. When the addition was complete, additional dibutyltindilaurate (2 drops) was added and the reaction mixture was reheated to50° C. The completion of the reaction was confirmed by the disappearanceof the isocyanate peak at 2200 cm⁻¹ on the infrared spectrum. At the endof the reaction, methanol (about 100 mL) was added to quench anyresidual isocyanate groups. The solvent was removed in vacuo to reveal asoft, white, wax-like material. ¹H NMR (300 MHz, CDCl₃) δ6.47 (3H, dd,J=14.3, 6.8 Hz), 5.30-4.20 (br. m), 4.19 (3H, dd, J=14.3, 1.9 Hz),4.09-3.99 (12H, m), 4.00 (3H, dd, J=6.8, 1.9 Hz), 3.77-3.69 (6H, m),3.17-3.15 (12H, m), 1.72-1.26 (48H, m), 1.00-0.80 (3H, m).

EXAMPLE XIX

A compound of the formula

believed to have many different isomers, wherein each of the threebranches has four possibilities: (1) R₁, R₂, and R₅=CH₃; R₃, R₄, R₆, R₇,and R₈=H; (2) R₁, R₅, and R₆=CH₃; R₂, R₃, R₄, R₇, and R₈=H; (3) R₃, R₇,and R₈=CH₃; R₁, R₂, R₄, R₅, and R₆=H; (4) R₃, R₄, and R₇=CH₃; R₁, R₂,R₅, R₆, and R₈=H; (5) R₉, R₁₀, and R₁₃=CH₃; R₁₁, R₁₂, R₁₄, R₁₅, andR₁₆=H; (6) R₉, R₁₃, and R₁₄=CH₃; R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆=H; (7) R₁₁,R₁₅, and R₁₆=CH₃; R₉, R₁₀, R₁₂, R₁₃, and R₁₄=H; (8) R₁₁, R₁₂, andR₁₅=CH₃; R₉, R₁₀, R₁₃, R₁₄, and R₁₆=H; (9) R₁₇, R₁₈, and R₂₁=CH₃; R₁₉,R₂₀, R₂₂, R₂₃, and R₂₄=H; (10) R₁₇, R₂₁, and R₂₂=CH₃; R₁₈, R₁₉, R₂₀,R₂₃, and R₂₄=H; (11) R₁₉, R₂₃, and R₂₄=CH₃; R₁₇, R₁₈, R₂₀, R₂₁, andR₂₂=H; (12) R₁₉, R₂₀, and R₂₃=CH₃; R₁₇, R₁₈, R₂₁, R₂₂, and R₂₄=H, oneisomer of which has the formula

was prepared as follows. To a 1 L three neck flask equipped with a stirbar, dropping funnel reflux condenser, stopper, and argon inlet wasadded trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and2,4,4-isomers, 33.55 g, 0.16 mol, obtained from Sigma-Aldrich,Milwaukee, Wis.) and anhydrous tetrahydrofuran (300 mL). To the stirringsolution was added 1,4-butanediol vinyl ether (17.65 g, 0.15 mol,obtained from Sigma-Aldrich) in anhydrous tetrahydrofuran (150 mL) viathe dropping funnel. When the addition was complete, dibutyltindilaurate (0.96 g, 1.52 mmol, obtained from Sigma-Aldrich) was added.The reaction mixture was heated to 50° C. After 15 min, the reactionmixture was cooled to room temperature and trimethylolpropane (8.97 g,67 mmol, obtained from Sigma-Aldrich) in anhydrous tetrahydrofuran (50mL) was added slowly, dropwise to the reaction mixture. When theaddition was complete, additional dibutyltin dilaurate (2 drops) wasadded and the reaction mixture was reheated to 50° C. The completion ofthe reaction was confirmed by the disappearance of the isocyanate peakat 2200 cm⁻¹ on the infrared spectrum. At the end of the reaction,methanol was added to quench any residual isocyanate groups. The solventwas removed in vacuo to reveal a highly viscous, pale yellow oil. ¹H NMR(300 MHz, CDCl₃) δ6.47 (3H, dd, J=14.3, 6.8 Hz), 5.59-4.72 (6H, br. m),4.19 (3H, dd, J=14.3, 1.9 Hz), 4.08 (12H, br. s), 3.99 (3H, dd, J=6.8,1.9 Hz), 3.73-3.68 (6H, m), 3.14-2.78 (12H, m), 1.85 (12H, br. s),1.85-1.25 (47H, m).

EXAMPLE XX

A compound of the formula

was prepared as follows. To a 1 L three neck flask equipped with a stirbar, dropping funnel reflux condenser, stopper, and argon inlet wasadded 1,6-diisocyanatohexane (26.84 g, 0.16 mol, obtained fromSigma-Aldrich, Milwaukee, Wis.) and anhydrous tetrahydrofuran (300 mL).To the stirring solution was added 1,4-butanediol vinyl ether (17.65 g,0.15 mol, obtained from Sigma-Aldrich) in anhydrous tetrahydrofuran (150mL) via the dropping funnel. When the addition was complete, dibutyltindilaurate (0.97 g, 1.5 mmol, obtained from Sigma-Aldrich) was added. Thereaction mixture was heated to 50° C. When 50% of the isocyanate groupswere consumed (peaks at about δ3.30 and δ3.16 in an approximately 1:1ratio on the ¹H NMR spectrum; reaction time was approximately 15minutes), the reaction mixture was cooled to room temperature anddi(trimethylolpropane) (11.01 g, 44 mmol, obtained from Sigma-Aldrich)in anhydrous tetrahydrofuran (200 mL) was added slowly, dropwise to thereaction mixture. When the addition was complete, additional dibutyltindilaurate (8 drops) was added and the reaction mixture was reheated to50° C. The completion of the reaction was confirmed by the disappearanceof the isocyanate peak at 2200 cm⁻¹ on the infrared spectrum. At the endof the reaction, methanol was added to quench any residual isocyanategroups. The solvent was removed in vacuo to reveal a white solid. ¹H NMR(300 MHz, CDCl₃) δ6.49 (4H, dd, J=14.3, 6.8 Hz), 5.30-4.55 (8H, br. m),4.20 (4H, dd, J=14.3, 1.9 Hz), 4.08 (16H, br. s), 3.99 (4H, dd, J=1.9,6.8 Hz), 3.77-3.68 (8H, m), 3.21-3.09 (16H, m), 1.72 (16H, br. s),1.49-1.15 (38H, m), 0.95-0.80 (6H, m).

EXAMPLE XXI

A compound of the formula

believed to have many different isomers, wherein each of the threebranches has four possibilities: (1) R₁, R₂, and R₅=CH₃; R₃, R₄, R₆, R₇,and R₈=H; (2) R₁, R₅, and R₆=CH₃; R₂, R₃, R₄, R₇, and R₈=H; (3) R₃, R₇,and R₈=CH₃; R₁, R₂, R₄, R₅, and R₆=H; (4) R₃, R₄, and R₇=CH₃; R₁, R₂,R₅, R₆, and R₈=H; (5) R₉, R₁₀, and R₁₃=CH₃; R₁₁, R₁₂, R₁₄, R₁₅, andR₁₆=H; (6) R₉, R₁₃, and R₁₄=CH₃; R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆=H; (7) R₁₁,R₁₅, and R₁₆=CH₃; R₉, R₁₀, R₁₂, R₁₃, and R₁₄=H; (8) R₁₁, R₁₂, andR₁₅=CH₃; R₉, R₁₀, R₁₃, R₁₄, and R₁₆=H; (9) R₁′, R₂′, and R₅′=CH₃; R₃′,R₄′, R₆′, R₇′, and R₈′=H; (10) R₁′, R₅′, and R₆′=CH₃; R₂′, R₃′, R₄′,R₇′, and R₈′=H; (11) R₃′, R₇′, and R₈′=CH₃; R₁′, R₂′, R₄′, R₅′, andR₆′=H; (12) R₃′, R₄′, and R₇′=CH₃; R₁′, R₂′, R₅′, R₆′, and R₈′=H; (13)R₉′, R₁₀′, and R₁₃′=CH₃; R₁₁′, R₁₂′, R₁₄′, R₁₅′, and R₁₆′=H; (14) R₉′,R₁₃′, and R₁₄′=CH₃; R₁₀′, R₁₁′, R₁₂′, R₁₅′, and R₁₆′=H; (15) R₁₁′, R₁₅′,and R₁₆′=CH₃; R₉′, R₁₀′, R₁₂, R₁₃′, and R₁₄′=H; (16) R₁₁′, R₁₂′, andR₁₅′=CH₃; R₉′, R₁₀′, R₁₃′, R₁₄′, and R₁₆′=H (wherein the primed Rvariables represent the second occurrence of these —H or —CH₃ groups,since the moieties occur on each side of the center oxygen atom), oneisomer of which has the formula

was prepared as follows. To a 1 L three neck flask equipped with a stirbar, dropping funnel reflux condenser, stopper, and argon inlet wasadded trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and2,4,4-isomers, 33.08 grams, 0.16 mol; obtained from Sigma-Aldrich,Milwaukee, Wis.) and tetrahydrofuran (300 mL). To the stirring solutionwas added 1,4-butanediol vinyl ether (17.40 grams, 0.15 mol; obtainedfrom Sigma-Aldrich) in anhydrous tetrahydrofuran (150 mL) via thedropping funnel. When the addition was complete, dibutyltin dilaurate(0.95 gram, 1.5 mmool; obtained from Sigma-Aldrich) was added. Thereaction mixture was heated to 50° C. After 15 min, the reaction mixturewas cooled to room temperature and di(trimethylolpropane) (12.75 grams;51 mmol; obtained from Sigma-Aldrich) in anhydrous tetrahydrofuran (200mL) was added slowly, dropwise to the reaction mixture. When theaddition was complete, additional dibutyltin dilaurate (8 drops) wasadded and the reaction mixture was reheated to 50° C. The completion ofthe reaction was confirmed by the disappearance of the isocyanate peakat 2200 cm⁻¹ on the infrared spectrum. At the end of the reaction,methanol (about 100 ml) was added to quench any residual isocyanategroups. The solvent was removed in vacuo to reveal a pale yellow oil.

¹H NMR (300 MHz, CDCl₃) δ6.46 (4H, dd, J=14.3, 6.8 Hz), 5.24-4.56 (8H,br. m), 4.18 (4H, dd, J=14.3, 1.9 Hz), 4.07 (16H, s), 3.98 (4H, dd,J=6.8, 1.9 Hz), 3.71-3.67 (8H, m), 3.35-2.80 (20H, m), 1.80-1.60 (16H,m), 1.60-0.81 (66H, m).

INK EXAMPLE A

To a glass beaker was added 5.8 g ofbis[4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamate (mixture of2,2,4- and 2,4,4-isomers, prepared as described in Example XVII), 3.0 gof 1-octadecanol (obtained from Sigma-Aldrich, Milwaukee, Wis.), 0.1 gof the polyurethane synthesized in Example XVIII, and 1.0 g of R-GEN®BF-1172 (cationic photoinitiator; substituted triarylsulfoniumhexafluorophosphate salt in propylene carbonate as a 40% solution;obtained from Chitec Chemical Co., Ltd., Taiwan, R.O.C.), and thereaction mixture was stirred until homogeneous (about 0.5 hour). At thispoint, 0.1 g of Red Olefin Dye 24900 (obtained from Eastman ChemicalCompany, Kingsport, Tenn.) was added and the mixture was stirred withheating for an additional 1 hour. The ink was pipetted onto a glassslide as a liquid at 90° C. and exposed to UV light from a UV FusionLC-6B Benchtop Conveyor equipped with UV Fusion F300S Ultraviolet LampSystem employing an “H” bulb for about 5 seconds. The cured samples wereheated at 90° C. for 30 minutes and did not completely remelt,indicating that polymerization had occurred.

INK EXAMPLE B

To a glass beaker was added 5.8 g ofbis[4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamate (mixture of2,2,4- and 2,4,4-isomers, prepared as described in Example XVIII), 3.0 gof 1-octadecanol (obtained from Sigma-Aldrich, Milwaukee, Wis.), 0.1 gof the polyurethane synthesized in Example XIX, and 1.0 g of R-GEN®BF-1172 (cationic photoinitiator; substituted triarylsulfoniumhexafluorophosphate salt in propylene carbonate as a 40% solution;obtained from Chitec Chemical Co., Ltd., Taiwan, R.O.C.), and thereaction mixture was stirred until homogeneous (about 0.5 hour). At thispoint, 0.1 g of Red Olefin Dye 24900 (obtained from Eastman ChemicalCompany, Kingsport, Tenn.) was added and the mixture was stirred withheating for an additional 1 hour. The ink was pipetted onto a glassslide as a liquid at 90° C. and exposed to UV light from a UV FusionLC-6B Benchtop Conveyor equipped with UV Fusion F300S Ultraviolet LampSystem employing an “H” bulb for about 5 seconds. The cured samples wereheated at 90° C. for 30 minutes and did not completely remelt,indicating that polymerization had occurred.

INK EXAMPLE C

To a glass beaker was added 5.8 g ofbis[4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamate (mixture of2,2,4- and 2,4,4-isomers, prepared as described in Example XVIII), 3.0 gof 1-octadecanol (obtained from Sigma-Aldrich, Milwaukee, Wis.), 0.1 gof the polyurethane synthesized in Example XX, and 1.0 g of R-GEN®BF-1172 (cationic photoinitiator; substituted triarylsulfoniumhexafluorophosphate salt in propylene carbonate as a 40% solution;obtained from Chitec Chemical Co., Ltd., Taiwan, R.O.C.), and thereaction mixture was stirred until homogeneous (about 0.5 hour). At thispoint, 0.1 g of Red Olefin Dye 24900 (obtained from Eastman ChemicalCompany, Kingsport, Tenn.) was added and the mixture was stirred withheating for an additional 1 hour. The ink was pipetted onto a glassslide as a liquid at 90° C. and exposed to UV light from a UV FusionLC-6B Benchtop Conveyor equipped with UV Fusion F300S Ultraviolet LampSystem employing an “H” bulb for about 5 seconds. The cured samples wereheated at 90° C. for 30 minutes and did not completely remelt,indicating that polymerization had occurred.

INK EXAMPLE D

To a glass beaker was added 5.8 g ofbis[4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamate (mixture of2,2,4- and 2,4,4-isomers, prepared as described in Example XVIII), 3.0 gof 1-octadecanol (obtained from Sigma-Aldrich, Milwaukee, Wis.), 0.1 gof the polyurethane synthesized in Example XXI, and 1.0 g of R-GEN®BF-1172 (cationic photoinitiator; substituted triarylsulfoniumhexafluorophosphate salt in propylene carbonate as a 40% solution;obtained from Chitec Chemical Co., Ltd., Taiwan, R.O.C.), and thereaction mixture was stirred until homogeneous (about 0.5 hour). At thispoint, 0.1 g of Red Olefin Dye 24900 (obtained from Eastman ChemicalCompany, Kingsport, Tenn.) was added and the mixture was stirred withheating for an additional 1 hour. The ink was pipetted onto a glassslide as a liquid at 90° C. and exposed to UV light from a UV FusionLC-6B Benchtop Conveyor equipped with UV Fusion F300S Ultraviolet LampSystem employing an “H” bulb for about 5 seconds. The cured samples wereheated at 90° C. for 30 minutes and did not completely remelt,indicating that polymerization had occurred.

INK EXAMPLE E

To a glass beaker was added 6.9 g ofbis[4-(vinyloxy)butyl]trimethyl-1,6-hexanediylbiscarbamate (mixture of2,2,4- and 2,4,4-isomers, prepared as described in Example XVIII), 1.0 gof the polyurethane synthesized in Example XX, 1.0 g of4-(vinyloxy)butyl stearate (obtained from Morflex Inc., Greensboro, N.C.as VEctomer® 3080), and 1.0 g of R-GEN® BF-1172 (cationicphotoinitiator; substituted triarylsulfonium hexafluorophosphate salt inpropylene carbonate as a 40% solution; obtained from Chitec ChemicalCo., Ltd., Taiwan, R.O.C.), and the reaction mixture was stirred untilhomogeneous (about 0.5 hour). At this point, 0.1 g of Red Olefin Dye24900 (obtained from Eastman Chemical Company, Kingsport, Tenn.) wasadded and the mixture was stirred with heating for an additional 1 hour.The ink was pipetted onto a glass slide as a liquid at 90° C. andexposed to UV light from a UV Fusion LC-6B Benchtop Conveyor equippedwith UV Fusion F300S Ultraviolet Lamp System employing an “H” bulb forabout 5 seconds. The cured samples were heated at 90° C. for 30 minutesand did not completely remelt, indicating that polymerization hadoccurred.

Inks A through E are jetted using a PHASER® 860 printer modified tochange the intermediate transfer drum temperature, paper preheatingtemperature, and ink heating temperature and printed at 103° C. directlyonto paper attached to an intermediate transfer member at 30° C. It isbelieved that the inks will be successfully jetted onto LUSTROGLOSS®(Sappi Warren Papers) glossy coated paper and HAMMERMILL® (InternationalPaper) and XEROX® 4024 uncoated papers. It is believed that in eachcase, an increase in robustness will be observed when the prints areexposed to light from a UV Fusion LC-6B Benchtop Conveyor equipped withUV Fusion F300S Ultraviolet Lamp System employing an “H” bulb for about10 seconds.

Other embodiments and modifications of the present invention may occurto those of ordinary skill in the art subsequent to a review of theinformation presented herein; these embodiments and modifications, aswell as equivalents thereof, are also included within the scope of thisinvention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A phase change ink comprising a colorant, an initiator, and a phase:change ink carrier, said carrier comprising (A) a firstisocyanate-derived compound which is the reaction product of a mixturecomprising (1) an isocyanate; and (2) a component comprising (a) analcohol having at least one ethylenic unsaturation; (b) an amine havingat least one ethylenic unsaturation; (c) an acid having at least oneethylenic unsaturation; or (d) mixtures thereof, (B) a secondisocyanate-derived compound which is the reaction product of (1) adiisocyanate; (2) a monoalcohol having exactly one hydroxyl group andhaving at least one ethylenic unsaturation; and (3) a polyol having twoor more hydroxyl groups, (C) an optional phase change inducingcomponent, said phase change inducing component containing at least onehydroxyl group, said phase change inducing component having a meltingpoint of about 40° C. or higher, and (D) an optional curable viscositymodifying ester, said ink being curable upon exposure to ultravioletradiation.
 2. An ink according to claim 1 wherein the polyol has threeor more hydroxyl groups.
 3. An ink according to claim 1 wherein thepolyol is of the formula R₇(OH)_(z) wherein z is an integer representingthe number of hydroxyl groups and is at least about 2 and R₇ is (i) analkyl group (including linear and branched, saturated and unsaturated,cyclic and acyclic, and substituted and unsubstituted alkyl groups, andwherein hetero atoms either may or may not be present in the alkylgroup), (ii) an aryl group (including substituted and unsubstituted arylgroups, and wherein hetero atoms either may or may not be present in thearyl group), (iii) an arylalkyl group (including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, saturated or unsaturated,cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms either may or may not be present in either the aryl or the alkylportion of the arylalkyl group), (iv) an alkylaryle group (includingsubstituted and unsubstituted alkylaryl groups, wherein the alkylportion of the alkylaryl group can be linear or branched, saturated orunsaturated, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group), or (v) an oligomeric orpolymeric group.
 4. An ink according to claim 3 wherein R₇ is an alkylgroup.
 5. An ink according to claim 1 wherein the polyol istrimethylolpropane, di(trimethylolpropane), 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16hexandecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19nonadecanediol, 1,20-eicosanediol, 1,22-docosanediol,1,25-pentacosanediol, trimethylolethane, pentaerythritol,pentaerythritol ethoxylate, pentaerythritol propoxylate, polypropyleneglycol, polyethylene glycol, polyethylene adipate, poly(tetramethyleneether)glycol, glycerol, or mixtures thereof.
 6. An ink according toclaim 1 wherein the second isocyanate-derived compound is (a) of theformula

(b) of the formula

(c) of the formula

wherein each branch of the compound has the following fourpossibilities: (1) R₁, R₂, and R₅=CH₃; R₃, R₄, R₆, R₇, and R₈=H; (2) R₁,R₅, and R₆=CH₃; R₂, R₃, R₄, R₇, and R₈=H; (3) R₃, R₇, and R₈=CH₃; R₁,R₂, R₄, R₅, and R₆=H; (4) R₃, R₄, and R₇=CH₃; R₁, R₂, R₅, R₆, and R₈=H;(5) R₉, R₁₀, and R₁₃=CH₃; R₁₁, R₁₂, R₁₄, R₁₅, and R₁₆=H; (6) R₉, R₁₃,and R₁₄=CH₃; R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆=H; (7) R₁₁, R₁₅, and R₁₆=CH₃;R₉, R₁₀, R₁₂, R₁₃, and R₁₄=H; (8) R₁₁, R₁₂, and R₁₅=CH₃; R₉, R₁₀, R₁₃,R₁₄, and R₁₆=H; (9) R₁₇, R₁₈, and R₂₁=CH₃; R₁₉, R₂₀, R₂₂, R₂₃, andR₂₄=H; (10) R₁₇, R₂₁, and R₂₂=CH₃; R₁₈, R₁₉, R₂₀, R₂₃, and R₂₄=H; (11)R₁₉, R₂₃, and R₂₄=CH₃; R₁₇, R₁₈, R₂₀, R₂₁, and R₂₂=H; (12) R₁₉, R₂₀, andR₂₃=CH₃; R₁₇, R₁₈, R₂₁, R₂₂, and R₂₄=H; (d) of the formula

wherein each branch of the compound has the following fourpossibilities: (1) R₁, R₂, and R₅=CH₃; R₃, R₄, R₆, R₇, and R₈=H; (2) R₁,R₅, and R₆=CH₃; R₂, R₃, R₄, R₇, and R₈=H; (3) R₃, R₇, and R₈=CH₃; R₁,R₂, R₄, R₅, and R₆=H; (4) R₃, R₄, and R₇=CH₃; R₁, R₂, R₅, R₆, and R₈=H;(5) R₉, R₁₀, and R₁₃=CH₃; R₁₁, R₁₂, R₁₄, R₁₅, and R₁₆=H; (6) R₉, R₁₃,and R₁₄=CH₃; R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆=H; (7) R₁₁, R₁₅, and R₁₆=CH₃;R₉, R₁₀, R₁₂, R₁₃, and R₁₄=H; (8) R₁₁, R₁₂, and R₁₅=CH₃; R₉, R₁₀, R₁₃,R₁₄, and R₁₆=H; (9) R₁′, R₂′, and R₅′=CH₃; R₃′, R₄′, R₆′, R₇′, andR₈′=H; (10) R₁′, R₅′, and R₆′=CH₃; R₂′, R₃′, R₄′, R₇′, and R₈′=H; (11)R₃′, R₇′, and R₈′=CH₃; R₁′, R₂′, R₄′, R₅′, and R₆′=H; (12) R₃′, R₄′, andR₇′=CH₃; R₁′, R₂′, R₅′, R₆′, and R₈′=H; (13) R₉′, R₁₀′, and R₁₃′=CH₃;R₁₁′, R₁₂′, R₁₄′, R₁₅′, and R₁₆′=H; (14) R₉′, R₁₃′, and R₁₄′=CH₃; R₁₀′,R₁₁′, R₁₂′, R₁₅′, and R₁₆′=H; (15) R₁₁′, R₁₅′, and R₁₆′=CH₃; R₉, R₁₀′,R₁₂′, R₁₃′, and R₁₄′=H; (16) R₁₁′, R₁₂′, and R₁₅′=CH₃; R₉′, R₁₀′, R₁₃′,R₁₄′, and R₁₆′=H, and wherein R₁′, R₂′, R₃′, R₄′, R₅′, R₆′, R₇′, R₈′,R₉′, R₁₀′, R₁₁′, R₁₂′, R₁₃′, R₁₄′, R₁₅′, and R₁₆′ represent the secondoccurrence of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃,R₁₄, R₁₅, and R₁₆; or (e) mixtures thereof.
 7. An ink according to claim1 wherein the second isocyanate-derived compound is present in the inkin an amount of at least about 0.5 percent by weight of the carrier. 8.An ink according to claim 1 wherein the second isocyanate-derivedcompound is present in the ink in an amount of no more than about 20percent by weight of the carrier.
 9. An ink according to claim 1 whereinthe monoalcohol having exactly one hydroxyl group and having at leastone ethylenic unsaturation is a vinyl ether of the formulaHO—R₃₃—OCH═CH₂ wherein R₃₃ is (i) an alkyl group (including linear andbranched, saturated and unsaturated, cyclic and acyclic, and substitutedand unsubstituted alkyl groups, and wherein hetero atoms either may ormay not be present in the alkyl group), (ii) an aryl group (includingsubstituted and unsubstituted aryl groups, and wherein hetero atomseither may or may not be present in the aryl group), (iii) an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, whereinthe alkyl portion of the arylalkyl group can be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms either may or may not be presentin either the aryl or the alkyl portion of the arylalkyl group), or (iv)an alkylaryl group (including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, saturated or unsaturated, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the alkylarylgroup).
 10. An ink according to claim 9 wherein R₃₃ is an alkyl group.11. An ink according to claim 1 wherein the ink contains a phase changeinducing component, said phase change inducing component containing atleast one hydroxyl group, said phase change inducing component having amelting point of about 40° C. or higher.
 12. An ink according to claim11 wherein the phase change inducing component is of the formulaR_(c)—OH wherein R_(c) is (i) an alkyl group, including linear andbranched, cyclic and acyclic, and substituted and unsubstituted alkylgroups, and wherein hetero atoms either may or may not be present in thealkyl group, (ii) an aryl group, including substituted and unsubstitutedaryl groups, and wherein hetero atoms either may or may not be presentin the aryl group, (iii) an arylalkyl group, including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup, or (iv) an alkylaryl group, including substituted andunsubstituted alkylaryl groups, wherein the alkyl portion of thealkylaryl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the alkylarylgroup.
 13. An ink according to claim 11 wherein the phase changeinducing component is 1,10-decanediol, 1,12-dodecanediol,1,2-dodecanediol, a mixture of linear primary alcohols having amolecular weight of at least about 350, a polycaprolactone diol,heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol,docosanol, dimer diols, Guerbet alcohols, hydrogenated castor oil, ormixtures thereof.
 14. An ink according to claim 11 wherein the phasechange inducing component is present in the ink in an amount of at leastabout 5 percent by weight of the carrier, and wherein the phase changeinducing component is present in the ink in an amount of no more thanabout 80 percent by weight of the carrier.
 15. An ink according to claim1 wherein the ink contains a curable viscosity modifying ester.
 16. Anink according to claim 15 wherein the curable viscosity modifying esteris of the formula

wherein R_(a) is (i) an alkyl group, including linear and branched,cyclic and acyclic, and substituted and unsubstituted alkyl groups, andwherein hetero atoms either may or may not be present in the alkylgroup, (ii) an arylalkyl group, including substituted and unsubstitutedarylalkyl groups, wherein the alkyl portion of the arylalkyl group canbe linear or branched, cyclic or acyclic, and substituted orunsubstituted, and wherein hetero atoms either may or may not be presentin either the aryl or the alkyl portion of the arylalkyl group, or (iii)an alkylaryl group, including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group, and wherein R_(b) is (i) analkyl group having at least one ethylenic unsaturation therein,including linear and branched, cyclic and acyclic, and substituted andunsubstituted alkyl groups, and wherein hetero atoms either may or maynot be present in the alkyl group, (ii) an arylalkyl group having atleast one ethylenic unsaturation therein, including substituted andunsubstituted arylalkyl groups, wherein the alkyl portion of thearylalkyl group can be linear or branched, cyclic or acyclic, andsubstituted or unsubstituted, and wherein hetero atoms either may or maynot be present in either the aryl or the alkyl portion of the arylalkylgroup, or (iii) an alkylaryl group having at least one ethylenicunsaturation therein, including substituted and unsubstituted alkylarylgroups, wherein the alkyl portion of the alkylaryl group can be linearor branched, cyclic or acyclic, and substituted or unsubstituted, andwherein hetero atoms either may or may not be present in either the arylor the alkyl portion of the alkylaryl group.
 17. An ink according toclaim 15 wherein the curable viscosity modifying ester isbis[4-(vinyloxy)butyl]adipate, 4-[(vinyloxy)butyl]stearate,tris[4-(vinyloxy)butyl]trimellitate,bis[4-(vinyloxy)butyl]dodecanedioate, or mixtures thereof.
 18. An inkaccording to claim 15 wherein the curable viscosity modifying ester ispresent in the phase change ink carrier in an amount of at least about 1percent by weight of the carrier and wherein the curable viscositymodifying ester is present in the phase change ink carrier in an amountof no more than about 30 percent by weight of the carrier.
 19. An inkaccording to claim 1 wherein the first isocyanate-derived compound isthe reaction product of an isocyanate and an alcohol.
 20. An inkaccording to claim 1 wherein the first isocyanate-derived compound isthe reaction product of an amine and an isocyanate.
 21. An ink accordingto claim 1 wherein the first isocyanate-derived compound is the reactionproduct of an acid and an isocyanate.
 22. An ink according to claim 1wherein the first isocyanate-derived compound is the reaction product ofan isocyanate and a mixture of an alcohol and an amine.
 23. An inkaccording to claim 1 wherein the first isocyanate-derived compound isthe reaction product of an isocyanate and a mixture of an acid and analcohol.
 24. An ink according to claim 1 wherein the firstisocyanate-derived compound is (a) of the formula

(b) of the formula

(c) of the formula

(d) of the formula

(e) of the formula

(f) of the formula

(g) of the formula

(h) of the formula

(i) of the formulae

and

(j) of the formula

(k) of the formula

(l) of the formula

(m) of the formula

(n) of the formula

(o) of the formula

or (p) mixtures thereof.
 25. A process which comprises (I) incorporatinginto an ink jet printing apparatus a phase change ink comprising acolorant, an initiator, and a phase change ink carrier, said carriercomprising (A) a first isocyanate-derived compound which is the reactionproduct of a mixture comprising (1) an isocyanate; and (2) a componentcomprising (a) an alcohol having at least one ethylenic unsaturation;(b) an amine having at least one ethylenic unsaturation; (c) an acidhaving at least one ethylenic unsaturation; or (d) mixtures thereof, (B)a second isocyanate-derived compound which is the reaction product of(1) a diisocyanate; (2) a monoalcohol having exactly one hydroxyl groupand having at least one ethylenic unsaturation; and (3) a polyol havingtwo or more hydroxyl groups, (C) an optional phase change inducingcomponent, said phase change inducing component containing at least onehydroxyl group, said phase change inducing component having a meltingpoint of about 40° C. or higher, and (D) an optional curable viscositymodifying ester, said ink being curable upon exposure to ultravioletradiation; (II) melting the ink; (III) causing droplets of the meltedink to be ejected in an imagewise pattern onto a substrate; and (IV)exposing the imagewise pattern to ultraviolet radiation.
 26. A processaccording to claim 25 wherein the substrate is a final recording sheetand droplets of the melted ink are ejected in an imagewise patterndirectly onto the final recording sheet and the imagewise pattern on thefinal recording sheet is exposed to ultraviolet radiation.
 27. A processaccording to claim 25 wherein the substrate is an intermediate transfermember and droplets of the melted ink are ejected in an imagewisepattern onto the intermediate transfer member followed by transfer ofthe imagewise pattern from the intermediate transfer member to a finalrecording sheet, and wherein the imagewise pattern on the finalrecording sheet is exposed to ultraviolet radiation.
 28. A processaccording to claim 27 wherein the intermediate transfer member is heatedto a temperature above that of the final recording sheet and below thatof the melted ink in the printing apparatus.